Fire-resistant sheetlike molding, fire-resistant laminate for covering steel, fire-resistant structure for wall, and method for constructing fire-resistant steel and fire-resistant wall

ABSTRACT

A fire-resistant sheet-like molded article having flame resistance and capable of producing good fire-resisting properties as the result of residues after combustion having sufficient shape-retaining property and, further, having good workability, a fire-resistant laminate for covering structural steels and a fire-resistant structural material for walls in which said molded article is used as well as a method of fabricating a fire-resistant structural steel and a fire-resistant wall. A fire resistant sheet-like molded article comprising a resin composition and having the-relationship between the initial thickness t (mm) and temperature difference ΔT (° C.) between one side and the reverse side after heating of said one side at 500° C. for 1 hour as represented by: 
     
       
         ΔT≧0.015t 4 −0.298t 3 +1.566t 2 +30.151t, and 
       
     
     having the initial bulk density at 25° C. of 0.8 to 2.0 g/cm 3  and the bulk density after 1 hour of heating at 500° C. of 0.05 to 0.5 g/cm 3 .

TECHNICAL FIELD

The present invention relates to a fire-resistant sheet-like moldedarticle suited for use in fields where heat insulation andfire-resistant properties are required, in particular for use as abuilding material, to a fire-resistant laminate for covering astructural steel and a fire-resistant structural material for wall inwhich said molded article is used, and to a method of fabricating afire-resistant structural steel and a fire-resistant wall.

PRIOR ART

In the field of building materials, flame retardancy has been requiredunder the Building Standards Act and other regulations. On the otherhand, a resin material has come into wide use in the building industrywith the recent development of new uses and, accordingly, afire-resistant resin material has been demanded.

Such a fire-resistant property includes not only the flame retardancy ofthe resin material itself but also its capability to prevent propagationof flames on the face side to the reverse side. The resin components andorganic components in a resin material are inherently combustible and/ormeltable and, therefore, it is an important performance requirement tokeep them from combusting or melting for a sufficiently long period oftime.

Thus, various technologies of compounding an inorganic component forproviding flame retardancy have been proposed. However, an inorganiccomponent lacking in self-adhesion properties tends to drop off, withthe result that flames are allowed to propagate round to the reverseside. It is therefore a problem to be solved how to maintain the shapewithout such drop-off for a sufficiently long time.

In Japanese Kokai Publication Hei-06-25476, there is disclosed a resincomposition comprising a polyolefin resin supplemented with redphosphorus or a phosphorus compound as well as thermally expandablegraphite. This resin composition has sufficient flame resistance,indeed, from the oxygen index viewpoint but, when molded into a sheetand used as a wall backing, for instance, it cannot meet the flameretardancy or fire protection test requirement that when the face sideis heated to 1,000° C., the temperature of the reverse side should notrise over 260° C.; it is thus insufficient in flame retardancy.Furthermore, in the flame retardancy or fire protection test, fragileresidues alone remain and others drop off, so that the functionality asa heat insulation layer is lost at an early stage, which is anotherproblem.

A resin composition comprising a urethane resin, ammonium polyphosphateand thermally expandable graphite has been proposed as an expansionmaterial for fire-resistant joints. However, this is used to prevent thepropagation of flames through around fire doors or joints of decorativepanels, and the range of application is thus restricted. In addition, ithas a problem, i.e. because a two-component curing method is employed,the technology is not called expedient, and the workability is poorbecause of the lack of tackiness.

A resin composition comprising a chloroprene polymer and vermiculite hasalso been proposed as a fire-resistant material. This is used to fill upgaps around the portions of walls or floors through which cables, ductsand the like are routed in the fire area to thereby prevent flames fromspreading. The range of its application is thus restricted. Anotherproblem is that its workability is poor because of the lack oftackiness.

A coat in composition comprising a binder resin, ammonium polyphosphate,an alcohol and a blowing agent has been proposed as a thermallyexpandable fire-resistant coating composition. However, this is rathersuited for application to structures whose appearance is required to bedecorative. In applications where any decorative character is notrequired but much importance is attached to fire-resistant properties,said composition cannot be considered suitable. Furthermore, since thisis in the form of a coating, its workability is poor and, for providingsufficient fire-resistant properties, it is necessary to apply saidcomposition in a considerable thickness and a technique therefor isrequired.

SUMMARY OF THE INVENTION

In view of the foregoing, the present invention has for its object toprovide a fire-resistant sheet-like molded article having flameresistance and capable of producing good fire-resisting properties asthe result of residues after combustion having sufficientshape-retaining property and, further, having good workability, afire-resistant laminate for covering structural steels and afire-resistant structure for walls in which said molded article is usedas well as a method of fabricating a fire-resistant structural steel anda fire-resistant wall.

In accordance with a first aspect of the present invention, there isprovided a fire-resistant sheet-like molded article comprising a resincomposition and having the relationship between the initial thickness t(mm) and temperature difference ΔT (° C.) between one side and thereverse side after heating of said one side at 500° C. for 1 hour asrepresented by:

ΔT≧0.015t⁴−0.298t³+1.566t²+30.151t, and

having the initial bulk density at 25° C. of 0.8 to 2.0 g/cm³ and thebulk density after 1 hour of heating at 500° C. of 0.05 to 0.5 g/cm³.

In accordance with a second aspect of the invention, there is provided afire-resistant sheet-like molded article comprising a resin composition,and having a breaking point and the load at breaking point of not lessthan 0.05 kg/cm² when it is subjected to volume expansion by heatingunder radiant heat flux of 50 kW/cm² for 30 minutes and then thecombustion residue is compressed at a rate of 0.1 cm/s.

In accordance with a third aspect of the invention, there is provided afire-resistant sheet-like molded article comprising a resin compositionand showing the thermal conductivity, after the volume expansion byheating under radiant heat flux of 50 kW/cm² for 30 minutes, of 0.01 to0.3 kcal/m·h·° C.

In accordance with a fourth aspect of the invention, there is provided afire-resistant sheet-like molded article comprising a resin compositionand showing the total endothermic value, when raising the temperature to600° C. at a rate of 10° C./min. by DSC, of not less than 100 J/g.

In accordance with a fifth aspect of the invention, there is provided afire-resistant sheet-like molded article comprising a resin compositionand having an initial thickness of 0.5 to 20 mm and tackiness enough tosupport itself under a load of 15 to 40 N/m of width at not more than180° C. for 30 minutes or longer.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic sectional view illustrating the first embodimentof the fire-resistant sheet-like molded article according to the presentinvention.

FIG. 2 is a schematic sectional view illustrating the second embodimentof the fire-resistant sheet-like molded article according to the presentinvention.

FIG. 3 is a schematic sectional view illustrating the third embodimentof the fire-resistant sheet-like molded article according to the presentinvention.

FIG. 4 is a schematic sectional view illustrating the fourth embodimentof the fire-resistant sheet-like molded article according to the presentinvention.

FIG. 5 is a graphic representation of the relationship between ΔT and tfor the fire-resistant sheet-like molded article according to the firstaspect of the present invention, wherein the ordinate denotes thedifference ΔT (° C.) between the temperature of the heated side and thetemperature of the reverse side and the abscissa denotes the initialthickness t (mm).

EXPLANATORY LIST OF SYMBOLS

1 wall material

2 fire-resistant sheet-like molded article

3 foamed material

4 incombustible material

5 ceiling

6 structural steel

7 frame for fixation.

DETAILED DESCRIPTION OF THE INVENTION

In the following, the present invention is described in detail.

The fire-resistant sheet-like molded article according to the firstaspect of the present invention shows a relationship between its initialthickness t (mm) and the temperature difference ΔT (° C.) between oneside and the reverse side after heating of said one side at 500° C. for1 hour as represented by:

ΔT≧0.015t⁴−0.298t³+1.566t²+30.151t.

In the above formula, ΔT represents the difference (° C.) between thetemperature of one side of the fire-resistant sheet-like molded articleand the temperature of the reverse side after heating said one side at500° C. for 1 hour and t represents the initial thickness (mm). The heatinsulation property of the residues formed upon expansion by heating canbe numerically expressed in terms of the above formula and a sufficientlevel of flame retardancy can be ensured.

Said fire-resistant sheet-like molded article has an initial bulkdensity of 0.8 to 2.0 g/cm³ at 25° C. By selecting the initial bulkdensity at 25° C. within the range of 0.8 to 2.0 g/cm³, it is possiblefor the fire-resistant sheet-like molded article to have excellentworkability without any substantial impairment of the thermalinsulating, fire-resisting and other physical properties required of thefire-resistant sheet-like molded article.

If the initial bulk density at 25° C. is lower than 0.8 g/cm³, it isimpossible to incorporate in the resin composition, a expandablematerial, a carbonizing agent, an incombustible filler and otheradditives in sufficient amounts and, as a result, the expansion ratioand amount of residues after heating will become insufficient and itwill be impossible to form a fire-resisting and heat-insulating layer.If the initial bulk density at 25° C. is higher than 2.0 g/cm³, theresulting fire-resistant sheet-like molded article will have anexcessive weight, so that the workability in mounting or wrapping workswith large-area sheets will become lowered. Preferably, it is within therange of 1.0 to 1.8 g/cm³.

When heated at 500° C. for 1 hour, said fire-resistant sheet-like moldedarticle shows a bulk density of 0.05 to 0.5 g/cm³. If the bluk densityafter 1 hour of heating at 500° C. is lower than 0.05 g/cm³, voids willarise too abundantly, so that any fire-resisting and heat-insulatinglayer will not be formed due to disintegration during expansion. If itis higher than 0.5 g/cm³, the expansion ratio will be insufficient,sufficient fire-resisting effect cannot be produced, and it will beimpossible for a fire-resisting and heat-insulating layer to be formed.It is preferred that said density be within the range of 0.1 to 0.3g/cm³.

The present inventors found that when the relationship between ΔT and tis representable in terms of the formula

ΔT≧0.015t⁴−0.298t³+1.566t²+30.151t

and the initial bulk density at 25° C. is 0.8 to 2.0 g/cm³ and, further,the bulk density after 1 hour of heating at 500° C. is 0.05 to 0.5g/cm³, the fire-resistant sheet-like molded article after expansion byheating has a sufficient level of heat insulation characteristics andcan produce excellent fire-resisting effects, or else theheat-insulating effects are insufficient and sufficient fire-resistingeffects cannot be produced. The present invention has been completedbased on such findings.

The fire-resistant sheet-like molded article of the present inventionpreferably has an initial thickness of 0.5 to 20 mm. In the presentspecification, the term “initial thickness” means the thickness (mm) ofthe fire-resistant sheet-like molded article at 25° C. before expansionby heating.

If said initial thickness is less than 0.5 mm, the fire-resisting andheat-insulating layer formed after heating will be so thin that nosufficient fire-resisting effects will be produced. If it exceeds 20 mm,the resulting fire-resistant sheet-like molded article will becomeexcessive in weight, so that the mounting or wrapping works withlarge-area sheets will become difficult, hence the workability willbecome lowered and, in addition, the volume occupied by the moldedarticle will become large, whereby the effective space will be limited,causing inconvenience. A preferred range is 1 to 10 mm.

As for the fire-resistant sheet-like molded article according to thesecond aspect of the present invention, when it is subjected to volumeexpansion by heating under the radiant heat flux of 50 kW/cm² for 30minutes and then the combustion residue is compressed at the rate of 0.1cm/s, a breaking point is found and the load at breaking point is notless than 0.05 kg/cm². The term “breaking point” means the maximum pointof the load for causing displacement on the occasion of compression, atthe rate of 0.1 cm/s, of the combustion residue after volume expansionfor 30 minutes under the radiant heat flux of 50 kW/cm².

If no breaking point is found or if a breaking point is found but theload at breaking point is less than 0.05 kg/cm², the combustion residueformed by fire will be unable to maintain its shape but will drop off,hence will lose its function as an insulating layer at an early stage.

In the practice of the present invention, the initial thickness t (mm)of said fire-resistant sheet-like molded article and the thickness t′after 30 minutes of heating under the radiant heat flux of 50 kW/cm² arein the following relationship:

t′/t=1.1 to 20.

When t′/t is less than 1.1, the expansion ratio is insufficient, hencesufficient fire-resisting effects cannot be produced. When it is greaterthan 20, the expanded article cannot maintain its shape and form anymore but drops off. The above range is thus critical. The followingrange is preferred:

t′/t=1.5 to 15.

More preferred are those molded articles for which the thickness (t′)after heating under the above conditions is not less than twice thethickness (t) before heating.

The fire-resistant sheet-like molded article according to the thirdaspect of the present invention, when subjected to volume expansion for30 minutes under the radiant heat flux of 50 kW/cm², shows a thermalconductivity of 0.01 to 0.3 kcal/m·h·° C. When the thermal conductivityafter 30 minutes of volume expansion under the radiant heat flux of 50kW/cm² exceeds 0.3 kcal/m·h·° C., the heat insulation properties becomeinsufficient, so that no sufficient fire-resisting effects can beproduced. Those molded articles showing a thermal conductivity less than0.01 kcal /m·h·° C. cannot be produced using a mixture of organic andinorganic materials.

In the case of calcium silicate boards and the like which have so farbeen used as a refractory, it is possible to produce those which have athermal conductivity within the range of 0.01 to 0.3 kcal/m·h·° C. Onthe contrary, the fire-resistant sheet-like molded article of thepresent invention is characterized in that it expands in volume uponheating and shows, after volume expansion, a thermal conductivity of0.01 to 0.3 kcal/m·h·° C. Therefore, it has advantages in that, beforeexpansion by heating, it is thin and light and excellent in workabilityas compared with the conventional calcium silicate boards and, inaddition, leaves a larger effective space and that when heated, itexpands and thereby produces sufficient fire-resisting effects.

The fire-resistant sheet-like molded article according to the fourthaspect of the present invention, when heated to 600° C. at the rate of10° C./min. by DSC, shows a total endothermic value of not less than 100J/g. When it is not less than 100 J/g, the rate of temperature increasebecomes slow and better heat insulation effects are produced.

The fire-resistant sheet-like molded article according to the fifthaspect of the present invention has tackiness enough to support itselfunder a load of 15 to 40 N/m of width at 180° C. or below for 30 minutesor longer. A fire-resistant sheet-like molded article having suchtackiness can show fire-resisting property by supporting its own weightup to a high temperatures at which an expanded insulating layer isformed, so that the fire-resistant sheet-like molded article underheating will not fail to support its own weight before expansion,preventing it from breakage and dropping off.

The fire-resistant sheet-like molded article according to the presentinvention comprises a resin composition.

Said resin composition may be a resin composition (hereinafter sometimesreferred to as “resin composition 1”) containing a thermoplastic resin,a phosphorus compound, neutralized, thermally expandable graphite and aninorganic filler.

Said thermoplastic resin is not particularly restricted but includes,for example, polyolefin resins such as polypropylene resins andpolyethylene resins, poly(1-)butene resins, polypentene resins,polystyrene resins, acrylonitrile-butadiene-styrene resins,polycarbonate resins, polyphenylene ether resins, acrylic resins,polyamide resins, polyvinyl chloride resins and the like. Among them,polyolefin resins are preferred, and polyethylene resins are morepreferred.

Halogenated resins such as chloroprene resins and chlorinated butylresins are themselves high in flame-retarding effect, and undergocrosslinking as a result of dehalogenation upon heating, whereby thestrength of the residue after heating is improved. Hence, they arepreferred.

Those mentioned above as examples of the thermoplastic resin are veryflexible and have rubber-like properties and, therefore, the inorganicfiller mentioned above can be incorporated therein in highconcentrations, and the resulting fire-resistant sheet-like moldedarticle becomes soft and flexible.

Said polyethylene resins include, among others, ethylene homopolymers,ethylene-based copolymers and mixtures of these (co)polymers and,further, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylatecopolymers, ethylene-methacrylate copolymers and the like.

Said ethylene-based copolymers include, among others, copolymers ofethylene, which is the main component, and other α-olefin(s). As saidα-olefin(s), there may be mentioned, for example, 1-hexene,4-methyl-1-pentene, 1-octene, 1-butene and 1-pentene.

As said ethylene homopolymers and said copolymers of ethylene and otherα-olefin(s), there may be mentioned those produced by polymerizationusing, as a polymerization catalyst, a Ziegler-Natta catalyst, vanadiumcatalyst or tetravalent transition metal-containing metallocene compoundor the like and, among them, polyethylene resins obtained by using atetravalent transition metal-containing metallocene compound as thecatalyst are preferred.

The tetravalent transition metal contained in said metallocene compoundis not particularly restricted but may be titanium, zirconium, hafnium,nickel, palladium, platinum or the like.

Said metallocene compound is a compound composed of said tetravalenttransition metal and one or more cyclopentadienyl rings or relatedcompounds coordinating as ligands.

As the polyethylene resins obtained by using such tetravalent transitionmetal-containing metallocene compound as the catalyst, there may bementioned Dow Chemical's “CGCT”, “Affinity” and “Engage” (trademarks);Exxon Chemical's “EXTRACT” (trademark), and other commercial products.

Said thermoplastic resins may be used singly or two or more of them maybe used in combination. For adjusting the resin melting viscosity,flexibility, tackiness and other properties, a blend of two or moreresins may be used as a base resin.

Furthermore, said thermoplastic resins may be subjected to crosslinkingor modification to an extent such that the fire-resisting effects of thefire-resistant sheet-like molded article of the present invention willnot be counteracted.

The time at which said thermoplastic resins are subjected tocrosslinking or modification is not particularly restricted butcrosslinking or modification may be performed at any stage. Thus, thethermoplastic resins crosslinked or modified in advance may be used, orthe thermoplastic resins may be crosslinked or modified simultaneouslywith the compounding of the phosphorus compound, inorganic filler andother components to be mentioned later herein, or crosslinking ormodification may be conducted after incorporation of other components inthe thermoplastic resins.

The method of crosslinking the thermoplastic resins is not restrictedbut includes crosslinking methods generally employed for thermoplasticresins, for example crosslinking methods using various crosslinkingagent or peroxides, for instance, and crosslinking methods usingelectron beam irradiation.

Said phosphorus compound is not particularly restricted but includes,among others, red phosphorus; various phosphoric acid esters, such astriphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, etc.; phosphoric acidmetal salts, such as sodium phosphate, potassium phosphate, magnesiumphosphate, etc.; ammonium polyphosphates; and compounds represented bythe general formula (1) shown below. Among them, ammonium polyphosphatesand compounds of general formula (1) are preferred, and ammoniumpolyphosphates are most preferred from the performance, safety, cost andother viewpoints.

In the above formula, R¹ and R³ each represents a hydrogen atom, astraight or branched alkyl group containing 1 to 16 carbon atoms or anaryl group containing 6 to 16 carbon atoms and R² represents a hydroxylgroup, a straight or branched alkyl group containing 1 to 16 carbonatoms, a straight or branched alkoxy group containing 1 to 16 carbonatoms, an aryl group containing 6 to 16 carbon atoms or an aryloxy groupcontaining 6 to 16 carbon atoms.

Said red phosphorus, when added in small amounts, can improve the flameretarding effects. As said red phosphorus, commercially available redphosphorus can be used but, from the viewpoint of moisture resistanceand safety from spontaneous ignition in the step of kneading, amongothers, red phosphorus particles surface-coated with a resin, forinstance, are judiciously used.

Said ammonium polyphosphates are not particularly restricted butinclude, for example, ammonium polyphosphate, melamine-modified ammoniumpolyphosphate and the like. As commercial products, there may bementioned, for example, Hoechst's “AP422” and “AP462” and SumitomoChemical's “Sumisafe P”.

The compounds represented by the above general formula (1) are notparticularly restricted but includes, among others, methylphosphonicacid, dimethyl methylphosphonate, diethyl methylphosphonate,ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid,2-methylpropylphosphonic acid, tert-butylphosphonic acid,2,3-dimethyl-butylphosphonic acid, octylphosphonic acid,phenylphosphonic acid, dioctyl phenylphosphonate, dimethylphosphinicacid, methylethylphosphinic acid, methylpropylphosphinic acid,diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid,diethylphenylphosphinic acid, diphenylphosphinic acid,bis(4-methoxyphenyl)phosphinic acid and the like. Among them,t-butylphosphinic acid is preferred because of high flame retardance,although it is expensive.

The phosphorus compounds mentioned above may be used singly or two ormore of them may be used in combination.

Said neutralized, thermally expandable graphite is a graphite speciesderived from thermally expandable graphite, which is a well knownsubstance, by neutralizing treatment. Said thermally expandable graphiteis a graphite intercalation compound formed by treatment of naturalflaky graphite, thermal decomposition graphite, kish graphite or likepowders with an inorganic acid, such as concentrated sulfuric acid,nitric acid, selenic acid or the like, and a strong oxidizing agent,such as concentrated nitric acid, perchloric acid, a perchlorate, apermanganate, a bichromate, hydrogen peroxide or the like. It is acompound retaining the layer structure of graphite.

The thermally expandable graphite obtained by the above acid treatmentis further neutralized with ammonia, an aliphatic lower amine, an alkalimetal compound, an alkaline earth metal compound or the like to give theabove-mentioned neutralized, thermally expandable graphite.

Said aliphatic lower amine is not particularly restricted but includes,among others, monomethylamine, dimethylamine, trimethylamine,ethylamine, propylamine, butylamine and the like.

Said alkali metal compound and alkaline earth metal compound are notparticularly restricted but include, for example, the hydroxides,oxides, carbonates, sulfates and organic acid salts of potassium,sodium, calcium, barium and magnesium.

As a commercial product of the above neutralized, thermally expandablegraphite, there may be mentioned, for example, Nippon Kasei Chemical's“CA-60S” and the like.

Said neutralized, thermally expandable graphite preferably has aparticle size of 20 to 200 mesh. When the particle size is smaller than200 mesh, the expansion ratio of graphite is small, hence desiredfire-resisting and heat-insulating layers cannot be obtained. When theparticle size is greater than 20 mesh, it is advantageous in that theexpansion ratio of graphite is high but the dispersibility thereof inthe step of kneading with the thermoplastic resin becomes poor,unavoidably leading to reductions in physical properties.

Said inorganic filler is not particularly restricted but includes, amongothers, metal oxides such as alumina, zinc oxide, titanium oxide,calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide,ferrite, etc.; hydrated inorganic compounds such as calcium hydroxide,magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc.; metalcarbonates such as basic magnesium carbonate, calcium carbonate,magnesium carbonate, zinc carbonate, strontium carbonate, bariumcarbonate, etc.; calcium salts such as calcium sulfate, gypsum fiber,calcium silicate, etc.; silica, diatomaceous earth, dawsonite, bariumsulfate, talc, clay, mica, montmorillonite, bentonite, activated clay,sepiolite, imogolite, sericite, glass fiber, glass beads, silica-basedballoons, aluminum nitride, boron nitride, silicon nitride, carbonblack, graphite, carbon fiber, carbon balloons, charcoal powder, variousmetal powders, potassium titanate, magnesium sulfate “MOS” (trademark),lead titanate zirconate, aluminum borate, molybdenum sulfide, siliconcarbide, stainless steel fiber, zinc borate, various ceramic powders,slag fiber, fish ash, dehydrated sludge and so forth. Among them,hydrated inorganic compounds and metal carbonates are preferred.

The hydrated inorganic compounds such as magnesium hydroxide andaluminum hydroxide are particularly advantageous in that the waterresulting from their dehydration upon heating absorbs heat to mitigatethe temperature increase and thereby provide for a high heat-resistingeffect and that the remaining oxides are served as combustion residuesand work as an aggregate to increase the residual strength. Magnesiumhydroxide and aluminum hydroxide have different temperature regions forproducing those effects of dehydration and, therefore, the combined usethereof is preferred since the temperature range for producing theeffects of dehydration is broadened and, as a result, more efficienttemperature rise-preventing effects are obtained.

The metal carbonates such as calcium carbonate and zinc carbonate areconsidered to promote the expansion through the reaction with ammoniumpolyphosphate when ammonium polyphosphate is used as the phosphoruscompound mentioned above. They also function as an effective aggregateand form residues high in shape-retaining ability after combustion.

Generally, the inorganic fillers function as aggregates and, therefore,it is considered that they contribute to improve the residue strengthand increase the heat capacity.

Said inorganic fillers may be used singly or two or more of them may beused in combination.

Said inorganic fillers may have a particle size of 0.5 to 400 μm. Whenthe amount of fillers is low, it is preferred that said inorganicfillers have a small particle size, since the performancecharacteristics depend on the dispersibility. When the particle size issmaller than 0.5 μm, however, secondary aggregation tends to occur andthe dispersibility decreases. In cases where the addition amount of theinorganic fillers is high, the viscosity of the resin compositionincreases, hence the moldability is decreased, with the increase infiller amount but the viscosity of the resin composition can be reducedby increasing the particle size; therefore, a large particle size ispreferred. If, however, the particle size exceeds 100 μm, the surfacecharacteristics of the moldings and the mechanical properties of theresin composition become decreased. A more preferred particle size isabout 1 to 50 μm.

As such inorganic fillers, there may be mentioned, for example, “H-42M”(product of Showa Denko), which is aluminum hydroxide and has a particlesize of 1 μm, “H-31” (product of Showa Denko), which is aluminumhydroxide with a particle size of 18 μm, “Whiton SB Red” (product ofShiraishi Calcium), which is calcium carbonate and has a particle sizeof 1.8 μm, “BF300” (product of Shiraishi Calcium), which is calciumcarbonate with a particle size of 8 μm, and so forth.

The combined use of an inorganic filler with a large particle size andone with a small particle size is more preferred. Such combined useenables higher levels of filling.

In the above resin composition 1, the total amount of the phosphoruscompound and neutralized, thermally expandable graphite is preferably 20to 300 parts by weight and the amount of the inorganic filler ispreferably 50 to 500 parts by weight, per 100 parts by weight of thethermoplastic resin.

When the total amount of the phosphorus compound and neutralized,thermally expandable graphite is less than 20 parts by weight, theamount of residues after heating becomes insufficient, leading tofailure in the formation of fire-resisting and heat-insulating layers.When it is above 300 parts by weight, the mechanical characteristics ofthe resulting fire-resistant sheet-like molded article become poor. Morepreferably, the total amount of the phosphorus compound and neutralized,thermally expandable graphite is 20 to 200 parts by weight.

If the amount of the inorganic filler is less than 50 parts by weight,the heat capacity will be low, causing a decrease in fire-resistingperformance. If it is above 500 parts by weight, the mechanicalproperties of the fire-resistant sheet-like molded article will bereduced.

The weight ratio between said inorganic filler and said phosphoruscompound is preferably about 1:1.

In the practice of the present invention in accordance with the first,third, fourth and fifth aspects of the present invention, the weightratio of said neutralized, thermally expandable graphite to saidphosphorus compound [(neutralized, thermally expandablegraphite)/(phosphorus compound)] is 0.01 to 9. By selecting said weightratio of neutralized, thermally expandable graphite to phosphoruscompound within the above range of 0.01 to 9, the combustion residue canhave shape-retaining properties and show high fire-resisting effects. Ifthe proportion of the neutralized, thermally expandable graphite is toohigh, the graphite expanded at the time of combustion will be scattered,hence sufficient expanded heat-insulating layer will not be obtained.Conversely, if the addition amount of the phosphorus compound isexcessive, the heat-insulating layer formation will become insufficient,hence sufficient heat-insulating effects will not be produced, either.

Even when said weight ratio of neutralized, thermally expandablegraphite to phosphorus compound [(neutralized, thermally expandablegraphite)/(phosphorus compound)] is 0.01 to 9, the shape retainingproperty may become insufficient, although a high expansion ratio can beattained if the proportion of the neutralized, thermally expandablegraphite is high. Therefore, in cases where said molded article is usedfor covering the under surface of a structural steel or the like, theresidue, which has become fragile, may possibly disintegrate and allowpenetration of flames. In that case, the weight ratio of neutralized,thermally expandable graphite to phosphorus compound is preferably 0.01to 2 from the viewpoint of shape retaining property on the occasion ofcombustion. More preferably, said ratio is 1/60 to 1/3, most preferably1/40 to 1/5.

The addition amount of said neutralized, thermally expandable graphitecan be selected based on the extent to which the shape retainingproperty is required in the application in question. To be concrete,when the proportion of the neutralized, thermally expandable graphite isnot more than 10 parts by weight, the shape retaining property isrelatively good and the combustion residue will never disintegrate.

In cases where it is used as a covering material, the fire-resistantsheet-like molded article may further be externally held by applying aunimflammable sheet material for fixation to thereby hold theheat-insulating layer.

In the practice of the present invention according to its second aspect,the weight ratio of neutralized, thermally expandable graphite tophosphorus compound [(neutralized, thermally expandablegraphite)/(phosphorus compound)] is 0.01 to 2. When the weight ratio ofneutralized, thermally expandable graphite to phosphorus compound isselected within said range of 0.01 to 2, the combustion residue canacquire good shape-retaining and high fire-resisting properties.

Presumably, the resin composition 1 mentioned above exhibits itsfire-resisting effect in the following manner, although the mechanismsare not so clear. Thus, upon heating, the neutralized, thermallyexpandable graphite expands and forms a heat-insulating layer andprevents heat transfer. On that occasion, the inorganic fillercontributes to increase the heat capacity. The phosphorus compound hasan ability to retain the shape of the expanded heat-insulating layer.

As the resin composition to be used in the practice of the presentinvention, there may be mentioned a resin composition (hereinaftersometimes referred to as “resin composition 2”) which comprises athermoplastic resin, a phosphorus compound, a hydroxyl-containinghydrocarbon compound and an inorganic filler.

Said thermoplastic resin and phosphorus compound are not particularlyrestricted but include, among others, those respectively mentioned aboveas examples with respect to resin composition 1.

Said inorganic filler is not particularly restricted but includes, amongothers, those specifically mentioned above in relation to resincomposition 1. In the resin composition 2, metal carbonates such ascalcium carbonate, magnesium carbonate, zinc carbonate and strontiumcarbonate, and calcium salts such as gypsum can increase a expansionratio and are therefore preferred. Hydrated inorganic compounds such asmagnesium hydroxide and aluminum hydroxide tend to give a low expansionratio in resin composition 2.

Said hydroxyl-containing hydrocarbon compound is not particularlyrestricted provided that it is a hydrocarbon compound containing ahydroxyl group(s) in a molecule but preferably a compound containing 1to 50 carbon atoms. Among others, a polyhydric alcohol containing two ormore hydroxyl groups in a molecule is preferred. However, to be suchthat, for polymers such as starch, the number of carbon atoms of theirmonomer units should be within said range.

As such polyhydric alcohols containing two or more hydroxyl groups in amolecule, there may be mentioned, for example, ethylene glycol,diethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol,1,6-hexanediol, monopentaerythritol, dipentaerythritol,tripentaerythritol, neopentaerythritol, sorbitol, inositol, mannitol,glucose, fructose, starch, cellulose and the like.

Such hydroxyl-containing hydrocarbon compounds may be used either singlyor two or more of them may be used in combination.

Preferred as said hydroxyl-containing hydrocarbon compound are thosecontaining at least two hydroxyl groups per molecule with a ratio of thenumber of hydroxyl groups to the number of carbon atoms [(number ofhydroxyl groups)/(number of carbon atoms)] of 0.2 to 2.0 and, morepreferred are those with a [(number of hydroxyl groups)/(number ofcarbon atoms)] of 0.7 to 1.5, typically pentaerythritols, sorbitol andmannitol. Among them, pentaerythritols are most preferred, since theycan show high carbonization-promoting effects owing to their highhydroxyl group content.

Said hydroxyl-containing hydrocarbon compound with a ratio of the numberof hydroxyl groups to the number of carbon atoms [(number of hydroxylgroups)/(number of carbon atoms)] of 0.2 to 2.0 undergoes dehydrationcondensation on the occasion of combustion and efficiently forms acarbonized layer. If said ratio [(number of hydroxyl groups)/(number ofcarbon atoms)] is less than 0.2, the carbon chain undergoesdecomposition rather than dehydration condensation on the occasion ofcombustion and therefore cannot sufficiently form a carbonized layer. Ifsaid ratio is higher than 2.0, the water resistance will markedlydecrease, although the carbonized layer formation is not affected.Reduced water resistance will produce problems in the step of watercooling of the molded article immediately after formation; for example,the hydroxyl-containing hydrocarbon compound may be eluded, or thehydroxyl-containing hydrocarbon compound may bleed out depending on thehumidity during storage of the molded article.

The phosphorus compound, hydroxyl-containing hydrocarbon compound andinorganic filler are compounded so that the total amount of said threecomponents be 50 to 900 parts by weight per 100 parts by weight of thethermoplastic resin.

When the total amount of said three components is smaller than 50 partsby weight, the amount of the residue after heating becomes insufficientand any fire-resisting and heat-insulating layer cannot be formed. Ifsaid amount exceeds 900 parts by weight, the mechanical properties ofthe fire-resistant sheet-like molded article will decrease. Said totalamount is preferably 100 to 700 parts by weight, more preferably 200 to500 parts by weight.

The weight ratio of said hydroxyl-containing hydrocarbon compound tosaid phosphorus compound [(hydroxyl-containing hydrocarboncompound)/(phosphorus compound)] is 0.05 to 20, from the viewpoint ofhigh fire-resisting property and shape retention of residue. When saidweight ratio is less than 0.05, the foamed heat-insulating layer becomesfragile and therefore cannot be useful. When it is above 20, the moldedarticle will not foam, hence no sufficient fire-resisting property willbe produced. Said ratio is preferably 0.3 to 10, more preferably 0.4 to5.

The weight ratio of said inorganic filler and said phosphorus compound[(inorganic filler)/(phosphorus compound)] is preferably 0.01 to 50 fromthe viewpoint of improved fire-resisting property and shape retention ofresidue, more preferably 0.3 to 15, most preferably 0.5 to 7. When saidweight ratio is less than 0.01, the foamed heat-insulating layer becomesfragile. If said weight ratio exceeds 50, the phosphorus compound, whichfunctions like a binder for the inorganic filler, will not function as abinder any longer, making the molding difficult; in addition, thefoaming upon heating will become insufficient, hence no sufficientfire-resisting effects will be obtained.

In the above resin composition 2, the phosphorus compound,hydroxyl-containing hydrocarbon compound and inorganic filler are usedcombinedly for the purpose of providing sufficient heat resistance,making the residue after combustion firm and thus retaining the shape ofthe residue. When the proportion of the phosphorus compound relative tothe hydroxyl-containing hydrocarbon compound and inorganic filler isexcessively high, the molded article expands greatly on the occasion ofcombustion and therefore the heat-insulating layer becomes fragile, sothat it becomes impossible to obtain a combustion residue sufficientlyfirm to an extent such that the material can stand withoutdisintegration even after combustion in its vertically standingposition.

When the proportion of said inorganic filler is excessive or theparticle size thereof is small, the oil absorption increases and theviscosity of the matrix increases on the occasion of foaming, so thatthe foaming is prevented, hence the heat-insulating effects becomeinsufficient. When the proportion of the inorganic filler is small, theviscosity is too low and the molded article does not foam but flows.

The fire-resisting effects of the resin composition 2 are presumablyproduced in the following manner, though not fully clear. Thus, uponheating, the phosphorus compound is dehydrated and foams and, at thesame time, functions also as a carbonization catalyst. Under thecatalytic action of the phosphorus compound, the hydroxyl-containinghydrocarbon compound forms a carbonized layer and forms aheat-insulating layer excellent in shape retaining property. Theinorganic filler plays an aggregate-like role and makes the carbonizedlayer more firm.

Further, as the resin composition to be used in the practice of thepresent invention, there may be mentioned a resin composition(hereinafter sometimes referred to as “resin composition 3”) comprisinga thermoplastic resin, a phosphorus compound, neutralized, thermallyexpandable graphite, a hydroxyl-containing hydrocarbon compound and aninorganic filler.

Said thermoplastic resin, phosphorus compound, neutralized, thermallyexpandable graphite and inorganic filler are not particularly restrictedbut include, among others, those respectively mentioned hereinabove inrelation to the resin composition 1. Preferred as the inorganic fillerare hydrated inorganic compounds, among others.

Said hydroxyl-containing hydrocarbon compound is not particularlyrestricted but includes, among others, those mentioned hereinabove inrelation to the resin composition 2.

The phosphorus compound, neutralized, thermally expandable graphite,hydroxyl-containing hydrocarbon compound and inorganic filler arepreferably compounded so that the total amount of said components be 50to 900 parts by weight per 100 parts by weight of the thermoplasticresin.

When the total amount of said three components is smaller than 50 partsby weight, the amount of the residue after heating becomes insufficientand any fire-resisting and heat-insulating layer cannot be formed. Ifsaid amount exceeds 900 parts by weight, the mechanical properties ofthe fire-resistant sheet-like molded article will decrease. Said totalamount is preferably 100 to 700 parts by weight, more preferably 200 to500 parts by weight.

The weight ratio of said neutralized, thermally expandable graphite tosaid phosphorus compound [(neutralized, thermally expandablegraphite)/(phosphorus compound)] is preferably 0.01 to 9. By selectingsaid weight ratio of neutralized, thermally expandable graphite tophosphorus compound within the range of 0.01 to 9, it is possible toobtain the combustion residue with shape-retaining and highfire-resisting properties. When the proportion of the neutralized,thermally expandable graphite is excessive, the graphite expanded on theoccasion of combustion scatters and no sufficient expandedheat-insulating layer can be obtained. On the other hand, when theproportion of the phosphorus compound is excessive, the heat-insulatinglayer formation is insufficient, so that no sufficient heat-insulatingeffects can be obtained.

From the viewpoint of shape retention on the occasion of combustion,said weight ratio of neutralized, thermally expandable graphite tophosphorus compound is preferably 0.01 to 5. Even when thefire-resistant resin composition itself is fire retardant, if the shaperetaining property is insufficient, the residue becomes fragile anddisintegrates, allowing penetration of flames. Therefore, the proportionof the neutralized, thermally expandable graphite can be selecteddepending on whether shape-retaining property is required or not in theintended use of the molded article. More preferably, said weight ratiois within the range of 0.01 to 2.

The weight ratio of said hydroxyl-containing hydrocarbon compound tosaid phosphorus compound [(hydroxyl-containing hydrocarboncompound)/(phosphorus compound)] is preferably 0.05 to 20, from theviewpoint of realization of high fire-resisting property and shaperetention of residue. When said weight ratio is less than 0.05, theexpanded layer becomes fragile and therefore cannot be useful. When itis above 20, the molded article will not expand, hence no sufficientfire-resisting effects will be produced. Said ratio is preferably 0.3 to10, more preferably 0.4 to 5.

The weight ratio of said inorganic filler to said phosphorus compound[(inorganic filler)/(phosphorus compound)] is preferably 0.01 to 50 fromthe viewpoint of improved fire-resisting property and shape retention ofresidue, more preferably 0.3 to 15, most preferably 0.5 to 7. When saidweight ratio is less than 0.01, the expanded layer becomes fragile. Ifsaid weight ratio exceeds 50, the phosphorus compound, which functionslike a binder for the inorganic filler, will not function as a binderany longer, making the molding difficult; in addition, the expansionupon heating will become insufficient, hence no sufficientfire-resisting property will be obtained.

The fire-resisting effects of the resin composition 3 are presumablyproduced in the following manner, though not fully clear. Thus, uponheating, the phosphorus compound is dehydrated and foams and, at thesame time, functions also as a carbonization catalyst. Under thecatalytic action of the phosphorus compound, the hydroxyl-containinghydrocarbon compound forms a carbonized layer and forms aheat-insulating layer excellent in shape retaining property. Theinorganic filler plays an aggregate-like role and makes the carbonizedlayer more firm. The neutralized, thermally expandable graphite expandson that occasion and forms a heat-insulating layer, and effectivelycontributes to prevent heat transfer.

Further, as the resin composition to be used in the practice of thepresent invention, there may be mentioned a resin composition(hereinafter sometimes referred to as “resin composition 4”) comprisinga thermoplastic resin, a phosphorus compound and a metal carbonate.

Said thermoplastic resin is not particularly restricted but includes,among others, those mentioned hereinabove in relation to the resincomposition 1.

Said phosphorus compound is not particularly restricted but may be anyof those phosphorus compounds which generate phosphoric acid underspecified radiant heat flux. Thus, for example, mention may be made ofthose mentioned hereinabove in relation to the resin composition 1. Saidradiant heat flux include heating at 200° C. in air, and said phosphoricacid to be generated includes phosphorous acid and hypophosphorous acidas well.

Said metal carbonate is not particularly restricted but includescarbonates of alkali metals, alkaline earth metals or metals of thegroup IIb of the periodic table. Specific examples are calciumcarbonate, strontium carbonate, zinc carbonate, magnesium carbonate andsodium carbonate. Among them, calcium carbonate, strontium carbonate andzinc carbonate are preferred.

Said resin composition 4 may further contain a hydrated inorganiccompound and/or a calcium salt.

Said hydrated inorganic compound is not particularly restricted butincludes, among others, aluminum hydroxide, magnesium hydroxide,hydrotalcite and the like.

Said calcium salt is not particularly restricted but includes, amongothers, calcium sulfate, gypsum, calcium diphosphate and the like.

Said phosphorus compound and metal carbonate are preferably compoundedso that the total amount thereof be 50 to 900 parts by weight per 100parts by weight of the thermoplastic resin. In cases where the resincomposition contains the hydrated inorganic compound and/or calciumsalt, the total amount of said phosphorus compound, metal carbonate andhydrated inorganic compound and/or calcium salt is preferably 50 to 900parts by weight per 100 parts by weight of the thermoplastic resin. Whensaid total amount is smaller than 50 parts by weight, the amount of theresidue after heating becomes insufficient and any fire-resisting andheat-insulating layer cannot be formed. If said amount exceeds 900 partsby weight, the mechanical properties of the fire-resistant sheet-likemolded article will decrease.

In cases where the resin composition contains the hydrated inorganiccompound and/or calcium salt, the total amount of said hydratedinorganic compound and/or calcium salt is preferably 1 to 70 parts byweight per 100 parts by weight of said metal carbonate. At an additionamount exceeding 70 parts by weight, no good shape-retaining property isproduced.

The weight ratio between said metal carbonate and phosphorus compound[(metal carbonate):(phosphorus compound)] is preferably 6:4 to 4:6. Byselecting said weight ratio between metal carbonate and phosphoruscompound within the range of 6:4 to 4:6, the resin composition can foamand expand and form firm and solid residue. An excessive proportion ofthe metal salt will result in failure to attain a sufficient expansionratio. An excessive proportion of the phosphorus compound will result indecreases in breaking strength and in mechanical properties of thefire-resistant sheet-like molded article.

In cases where the resin composition contains the hydrated inorganiccompound and/or calcium salt, the ratio between the total amount of saidmetal carbonate and hydrated inorganic compound and/or calcium salt tosaid phosphorus compound [(total of metal carbonate and hydratedinorganic compound and/or calcium salt):(phosphorus compound) ispreferably 6:4 to 4:6.

The fire-resisting effects of the resin composition 4 are presumablyproduced in the following manner, though not fully clear. Thus, thechemical reaction of polyphosphoric acid generated from the phosphoruscompound upon heating with the carbonate promotes the decarboxylationand ammonia releasing reactions. The phosphorus compound not onlygenerates polyphosphoric acid but also functions as a binder for thefoamed residue. The metal carbonate plays an aggregate-like role. Thehydrated inorganic compound and/or calcium salt is considered to play anaggregate-like role, like the metal carbonate.

Further, as the resin composition to be used in the practice of thepresent invention, there may be mentioned a resin composition(hereinafter sometimes referred to as “resin composition 5”) comprisinga thermoplastic resin, a phosphorus compound, neutralized, thermallyexpandable graphite, a hydrated inorganic compound and a metalcarbonate.

Said thermoplastic resin, phosphorus compound and neutralized, thermallyexpandable graphite are not particularly restricted but include, amongothers, those respectively mentioned hereinabove in relation to theresin composition 1.

Said hydrated inorganic compound and metal carbonate are notparticularly restricted but include, among others, those respectivelymentioned hereinabove in relation to the resin composition 4.

In said resin composition 5, said phosphorus compound and neutralized,thermally expandable graphite are preferably incorporated in a totalamount of 20 to 300 parts by weight, said metal carbonate in an amountof 10 to 500 parts by weight, and said hydrated inorganic compound in anamount of 10 to 500 parts by weight, per 100 parts by weight of thethermoplastic resin.

The weight ratio of said neutralized, thermally expandable graphite tosaid phosphorus compound [(neutralized, thermally expandablegraphite)/(phosphorus compound)] is preferably 0.01 to 9.

Said resin composition 5 is characterized in that it contains thehydrated inorganic compound and metal carbonate as the inorganic fillerin the resin composition 1 in specified proportions and, as a result,can attain further improvements in shape-retaining, flame-retardant andfire-resisting properties.

In the practice of the present invention, said resin compositionpreferably comprises a rubber composition. A resin compositioncomprising a rubber composition can be prepared by selecting at leastone of the following rubber compositions as the thermoplastic resin.

Said rubber compositions are not particularly restricted but include,among others, natural rubber (NR), isoprene rubber (IR), butadienerubber (BR), 1,2-polybutadiene rubber (1,2-BR), styrene-butadiene rubber(SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber(IIR), ethylene-propylene rubber (EPM, EPDM), chlorosulfonatedpolyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber(CO, ECO), polysulfide rubber (T), silicone rubber (Q), fluororubber(FKM, FZ), urethane rubber (U) and the like. These may be used singly ortwo ore more of them may be used combinedly. Additives generally used inrubber compositions may be used. From the viewpoint of providingtackiness, butyl rubber species are suited for use.

In the present invention, it is preferred that said resin compositionhas tackiness. The resin composition having tackiness is notparticularly restricted provided that it can provide the fire-resistantsheet-like molded article with properties enabling tack fixation. Saidresin composition having tackiness includes, in a wide sense, thoseresin compositions which have tackiness and/or adhesion properties.

By using a resin composition having tackiness, the fire-resistantsheet-like molded article is provided with tackiness and tack fixationthereof becomes possible and, when said article is used for coveringbuildings or the like, the workability thereof can be improved.

The resin composition of the present invention can be provided withtackiness by adding a tackifier per se known in the art to the abovethermoplastic resin or rubber compositions.

Said tackifier is not particularly restricted but includes, amongothers, tackifier resins, plasticizers, fats and oils, oligomers and thelike.

Said tackiner resins are not particularly restricted but include, amongothers, rosin, rosin derivatives, dammar, copal, coumarone, indeneresins, polyterpenes, nonreactive phenol resins, alkyl resins,petroleum-derived hydrocarbon resins, xylene resins, epoxy resins andthe like.

Although, when said plasticizers are used alone, it is difficult toprovide tackiness, they can contribute to further improvement intackiness when used in combination with the tackifier resins mentionedabove. Said plasticizers are not particularly restricted but include,among others, phthalate plasticizers, phosphate plasticizers, adipateplasticizers, sebacate plasticizers, ricinolate plasticizers, polyesterplasticizers, epoxy plasticizers, paraffin, chlorinated paraffin,process oil and the like.

Said fats and oils have the same effects as the plasticizers mentionedabove and can be used for providing plasticity and adjusting tackiness.Said fats and oils are not particularly restricted but include, amongothers, animal fats and oils, vegetable fats and oils, mineral oils,silicone oils and the like.

Said oligomers can be used not only for providing tackiness but also forimproving the low temperature resistance and adjusting the fluidity.Said oligomers are not particularly restricted but include, amongothers, oligomers corresponding to those given as examples of the rubbercompositions and poly(1-)butene type resin oligomers.

For increasing the holding power of said resin composition upon heating,there may be mentioned the method comprising increasing the viscosity ofthe rubber-like resin, the method comprising using an oligomer havinghigh molecular weight, and the method comprising using a tackifier resinwith a high softening point, among others.

As the method for increasing the viscosity of said rubber-like resincomposition, there may be mentioned the method comprising adding orsubstituting a high-viscosity rubber composition, the method comprisingcrosslinking the resin composition and the method comprising adding orsubstituting a crosslinked resin composition.

Said high-viscosity rubber composition preferably has a Mooney viscosityat 100° C. of not less than 40, more preferably not less than 45, mostpreferably not less than 55. For example, such butyl rubbers as Exxon's#065 (Mooney viscosity at 100° C.: 45) and Exxon's #268 (Mooneyviscosity at 125° C.: 51) and the like can be used.

As the method of crosslinking the resin composition, there may bementioned those methods used in crosslinking resins in general. The timeat which the resin composition is to be crosslinked or modified is notparticularly restricted but may be before or after the addition of thephosphorus compound, inorganic filler and/or other ingredients, orsimultaneous with such addition, for example, in an extruder. It is alsopossible to add a crosslinking agent and effect crosslinking aftermolding.

As the method using a crosslinking agent in cases where a doublebond-containing rubber such as butyl rubber or natural rubber isemployed, there may be mentioned sulfur vulcanization using sulfur,quinoid vulcanization using p-quinone dioxime or the like, sulfur donorvulcanization using morpholine disulfide or the like, resinvulcanization using a hydroxymethylated alkylphenol-formaldehyde resinor the like, and the method comprising adding a crosslinking agent suchas a peroxide such as benzyl peroxide or an azo compound such asazobisisobutyronitrile. It is also possible to effect crosslinking bycompounding a hydroxy group-modified rubber or an acid-modified rubberand combinedly using a known crosslinking agent such as a metal chelatecompound, polyisocyanate compound or polyvalent epoxy compound.

Said crosslinking agent is added preferably in an amount of 0.01 to 10parts by weight, more preferably 0.02 to 5 parts by weight, per 100parts of the thermoplastic resin to be crosslinked in the resincomposition. In certain cases, the addition of a catalyst such asstannous octoate may result in an increased rate of crosslinking, whichis favorable from the molding viewpoint.

When used in a crosslinked form, the resin composition of the presentinvention can improve the strength and holding power of thefire-resistant sheet-like molded article.

Useful in the above-mentioned method comprising adding or substituting acrosslinked resin are, for example, Exxon's butyl rubber Escorant 10(Moonery viscosity at 121° C.: 55) and the like.

In the above-mentioned method comprising using an oligomer having highmolecular weight, the use of an oligomer having a molecular weight ofnot less than 1,000 is preferred. Thus, for example, polybutene #300R(molecular weight: 1,450) and the like can be used.

In the above-mentioned method comprising using a tackifier resin with ahigh softening point, the use of a tackifier resin having a softeningpoint of not lower than 130° C. is preferred. Thus, for example,Idemitsu Petrochemical's I-Marv P140 (softening point: 140° C.) and thelike can be used.

It is also possible to improve the cohesive force of the fire-resistantsheet-like molded article by using a heat-curable rubber such as aphenol-modified rubber or an epoxy-modified rubber.

By using, as said rubber constituent, a rubber composition havingtackiness comprising 30 to 70 parts by weight of a rubber having aMooney viscosity at 100° C. of not less than 40, and 70 to 30 parts byweight of a liquid resin having an average molecular weight of 500 to10,000, the cohesive force, creep property and retaining property of thefire-resistant sheet-like molded article can favorably be improved. Byusing said rubber composition, the fire-resistant sheet-like moldedarticle, when heated, can be prevented from failing to hold its ownweight and consequent breaking and falling before expansion, andfire-resisting effects can be produced through holding of said ownweight even at the high temperature at which an expanded heat-insulatinglayer is formed.

For increasing the creep property of the fire-resistant sheet-likemolded article, a reinforcing substrate may be used for lamination. Saidreinforcing substrate is not particularly restricted provided that itcan reinforce the holding power of the fire-resistant sheet-like moldedarticle on the occasion of heating. Thus, there may be mentioned, forexample, paper, woven fabrics, nonwoven fabrics, films and wire nets.

As said paper, those known species such as kraft paper, Japanese paperand K linerboard can appropriately be used. The use of incombustiblepaper highly filled with aluminum hydroxide or calcium carbonate, orflame-retardant paper with a flame retardant compounded or superficiallyapplied, or inorganic fiber paper produced from rock wool, ceramic woolor glass fiber, or carbon fiber paper can contribute to furtherimprovements in flame retardancy.

Usable as said nonwoven fabrics are wet process nonwoven fabrics orcontinuous fiber nonwoven fabrics made of polypropylene, polyester,nylon or cellulose fiber or the like. When a nonwoven fabric having abasis weight of less than 7 g/m² is used, it may be readily broken bythe weight of the moldings in some instances. Therefore, nonwovenfabrics with a basis weight of 8 to 500 g/m² are preferred. Those havinga basis weight of 10 to 400 g/m² are more preferred.

Suited for use as said films are plastic films made of polyethylene,polypropylene, polyamide, polyester, nylon, acrylic or the like.

Usable as said wire nets are wire nets in general use and, further,metal laths and the like.

Such paper, woven fabric, nonwoven fabric, film, wire net or likesubstrate may be applied for lamination to one side of thefire-resistant sheet-like molded article of the present invention togive a singly tacky sheet with one side alone having tackiness, or maybe sandwiched between two tacky fire-resistant sheet-like moldedarticles to give a double tacky sheet with both sides having tackiness,or the double tacky sheet may further be provided, on one side, with asubstrate layer to give a single tacky sheet having a single tacky side.If said substrate is applied to both sides of the fire-resistantsheet-like molded article, the tackiness cannot be utilized at thefabrication.

In the present invention, the resin composition mentioned above mayfurther contain a fire retardant, antioxidant, metal inhibitor,antistatic, stabilizer, crosslinking agent, lubricant, softener, pigmentand/or the like incorporated in an amount such that the physicalproperties of said resin composition will not be impaired.

Said resin composition can be obtained by melting and kneading thecomponents mentioned above using a known kneading apparatus such as asingle- screw extruder, twin-screw extruder, Banbury mixer, kneadermixer or twin roll and the like.

Said resin composition can be molded into the fire-resistant sheet-likemolded article in the conventional manner, for example by press molding,calendar molding, or extrusion.

In the present specification, the fire-resistant sheet-like moldedarticle is not limited to a sheet-like molded article but may also belike a tape, for instance. Said term means all molded articles that areused in those fields in which heat insulation and flame retardancy arerequired and that satisfy the constituent elements of the presentinvention.

The fire-resistant sheet-like molded article of the present invention isnot limited in its field of application but may be used, for example, inthe automobile industry, in the electric and electronic industry, in thefield of building materials and in other areas where heat insulation andflame retardancy are required. The constituents of said resincomposition and the proportions thereof can be selected according to thefield of application.

In the field of building materials, the fire-resistant sheet-like moldedarticle of the present invention can judiciously be used as a coveringmaterial for structural steel, a composite wall material, ceiling,floor, or backing material for walls such as partition walls, amongothers. Those joint fillers which are used only for covering jointportions do not fall within the scope of the present invention, however.

The fire-resistant sheet-like molded article of the present inventioncan be used as a fire-resistant laminate for covering a structural steelwhich comprises a laminate comprising the fire-resistant sheet-likemolded article of the present invention and a sheet (a) capable ofholding the shape of the fire-resistant sheet-like molded articlewithout preventing the fire-resistant sheet-like molded article fromexpanding and capable of shielding said article from flames as joined bylamination.

Said sheet (a) is used for holding the shape of the fire-resistantsheet-like molded article without preventing the fire-resistantsheet-like molded article from expanding and for shielding said articlefrom flames. Said sheet (a) is not particularly restricted provided thatit can hold the shape of the fire-resistant sheet-like molded article,prevent penetration of flames and prevent combustion of thefire-resistant sheet-like molded article as resulting from directcontact of the fire-resistant sheet-like molded article with flames. Asexamples, there may be mentioned ceramic blankets; glass cloths;metallic sheets of iron, stainless steel, aluminum or the like.

The thickness of said sheet (a) is sufficient if the function ofshieling flames can be performed. Although it may vary depending on thenature of the material, it is preferably 0.1 to 10 times the initialthickness t (mm) of the fire-resistant sheet-like molded article. Whenit is less than 0.1 times, said sheet (a) may be broken, allowingpenetration of flames in fire. When it is more than 10 times, said sheet(a) may prevent the fire-resistant sheet-like molded article fromexpanding, causing a decrease in flame retardancy.

The above-mentioned fire-resistant laminate for covering a structuralsteel can be mounted on the structural steel to be covered in such amanner that the fire-resistant sheet-like molded article is in contactwith the structural steel and the sheet (a) is covered, and can be fixedby means of weld screws, nails, screws, bolts or the like. In that case,it may be mounted so as to extend along a face of the structural steel,or the fire-resistant laminate for covering a structural steel may beplaced on an external face of a box-shaped frame and, together with thebox as a whole, assembled with the structural steel.

In case of fire, said fire-resistant sheet-like molded article expandsand forms a fire-resisting and heat-insulating layer and said sheet (a)prevents flames from arriving at said fire-resistant sheet-like moldedarticle, so that heat transfer to the structural steel is prevented.

Said fire-resistant laminate for covering a structural steel issheet-like and therefore can easily be processed into an appropriateshape according to the shape of the structural steel to be covered.Furthermore, when the fire-resistant sheet-like molded article havingtackiness is used, the fire-resistant laminate for covering a structuralsteel of the present invention can temporarily be held on the structuralsteel surface until fixation with weld screws or the like, so that theworkability is excellent.

Fire-resistant structural steels, which comprise structural steelscovered with said fire-resistant laminate for covering a structuralsteel, can be judiciously used, for example, as beams, columns or thelike in steel-reinforced buildings.

As the method of fabricating the fire-resistant structural steels, whichcomprise structural steels covered with the fire-resistant sheet-likemolded article, there may be mentioned not only the method comprisingcovering the structural steels with said fire-resistant laminate forcovering a structural steel but also the method comprising covering thesurface of the structural steels with the fire-resistant sheet-likemolded article and then further covering thereon with the sheet (a)mentioned above.

Said structural steels are not particularly restricted but include,among others, structural steels made of H-, I-, C- (box)-shaped or likestructural steels.

The method of covering the surface of structural steels with theabove-mentioned fire-resistant sheet-like molded article and the sheet(a) is not particularly restricted but the method comprising effectingfixation with weld screws, nails, screws, bolts and/or the like., forexample, may be employed. Preferred is the method comprising effectingfixation of the fire-resistant sheet-like molded article and the sheet(a) simultaneously using common weld screws or the like. In this case,when the fire-resistant sheet-like molded article having tackiness isused, it becomes possible to retain the fire-resistant sheet-like moldedarticle on the surface of said structural steel throughout the timeduring which the covering of the structural steel with saidfire-resistant sheet-like molded article and further with said sheet (a)and fastening with weld screws are carried out, so that the workabilityis improved.

The fire-resistant sheet-like molded article of the present inventioncan also be used as a fire-resistant structural material for wall whichcomprises a board comprising, on at least one side thereof, thefire-resistant sheet-like molded article of the present invention.

Said board is not particularly restricted but includes, among others,steel sheets, stainless steel sheets, aluminum-zinc alloy sheets,aluminum sheets, calcium silicate boards, calcium carbonate boards,gypsum boards, pearlite cement boards, rock wool boards, slate boards,ALC boards, ceramic boards, mortar, precast concrete boards, cement-woodcomposites and the like.

The thickness of said board is preferably 0.5 to 100 mm. When it is lessthan 0.5 mm, no sufficient fire-resisting property can be produced. Whenit exceeds 100 mm, the workability becomes poor. Hence, the above rangeis critical. A more preferred thickness is 10 to 70 mm.

Said board preferably has a density of 0.2 to 2.5 gf/cm³. When it isless than 0.2 gf/cm³, the heat resistance becomes low, possibly allowingpenetration of flames. When it is above 2.5 gf/cm³, the workabilitybecomes poor. A more preferred range is 0.3 to 2.2 gf/cm³.

The above-mentioned fire-resistant sheet-like molded article expands bythe heat generated on the occasion of fire and thereby forms afire-resisting and heat-insulating layer, preventing heat transfer tothe reverse side of said board and, furthermore, even when the boardshrinks by the heat, followed by cracks formation or by gaps formationbetween such boards, said layer can prevent flames from propagatinground to the reverse side of said board.

In cases where the fire-resistant sheet-like molded article of thepresent invention is used for a fire-resistant structure material forwall, a layer of a material (b) capable of holding the shape of thefire-resistant sheet-like molded article without preventing saidfire-resistant sheet-like molded article from expanding may further beprovided on a layer of the fire-resistant sheet-like molded article.

Said material (b) is used to hold the shape, along the wall, of saidfire-resistant sheet-like molded article which expands upon heating.Said material (b) is not particularly restricted provided that it iscapable of holding said shape at 300° C. Thus, as examples, there may bementioned ceramic materials such as ceramic boards, ceramic blankets,etc.; metal sheets, wire nets or metal laths made of iron, stainlesssteel, aluminum, etc.; nonwoven fabrics; and paper. Among them, suchwire nets are suited for use, since they allow the fire-resistantsheet-like molded article to expand through meshes thereof.

It is also possible to provide a layer of the fire-resistant sheet-likemolded article further on the layer of said material (b) provided inadvance, so that said material (b) exists within a layer of thefire-resistant sheet-like molded articles.

The thickness of said material (b) is sufficient if the material (b) canperform its function, namely can hold the shape without preventingexpansion. Said thickness is preferably 0.05 to 10 times the thickness(t) of the fire-resistant sheet-like molded article before heating. Whenit is less than 0.5 times, the shape of said fire-resistant sheet-likemolded article cannot be held to a sufficient extent. If it exceeds 10times, the fire-resistant sheet-like molded article will be preventedfrom expanding, resulting in a decrease in flame retardancy.

The above-mentioned fire-resistant structural material for wall canjudiciously be used, for example, as a building material forconstituting a ceiling or floor material or an internal wall, such as apartition wall, or an external wall.

In the method for fabricating a fire-resistant wall using saidfire-resistant structural material for wall, at least one side of a wallmaterial is provided with the fire-resistant sheet-like molded article.

Said fire-resistant sheet-like molded article may be provided on oneside or both sides of the wall material. In the case of use as anexternal wall, one side alone is preferably provided with said article.For use as an internal wall such as a partition wall, both sides arepreferably provided with said article.

The method of fabricating said article is not restricted but the methodcomprising effecting fixation with nails, screws, bolts and/or the like,for example, may be employed. Further, by using the fire-resistantsheet-like molded article which has tackiness, it becomes possible tofix said fire-resistant sheet-like molded article to the wall materialwithout performing such a fixation method as mentioned above and itbecomes possible for a single person to perform the working with ease.

Then, the above-mentioned material (b) is provided on the fire-resistantsheet-like molded article now mounted on the wall material.

The method of fabricating said material (b) is not particularlyrestricted, but the method of effecting fixation using nails, screws,bolts or the like, for instance, may be employed.

As the method for fabricating the fire-resistant wall, it is alsopossible to use a unit composed of said fire-resistant sheet-like moldedarticle and the material (b) in advance and mount the same on a wallmaterial.

The method of fabricating the fire-resistant wall may be carried out ina step of producing fire-resistant walls in a factory or the like. It isalso possible to subject an existing wall to fire-resistant treatment byapplying said method to said existing wall.

BEST MODE FOR CARRYING OUT THE INVENTION

The modes of embodiment of the fire-resistant sheet-like molded articleof the present invention are illustrated with reference to the drawings.

An external wall backing material comprising a wall material 1 providedon one side thereof with the fire-resistant sheet-like molded article 2of the present invention is schematically shown in FIG. 1. In this case,the fire-resistant sheet-like molded article 2 may be provided on theexternal side thereof with a lath (wire net), SUS sheet or glass fibersheet or the like as a presser member for preventing from dropping. Whenthe fire-resistant sheet-like molded article is one having tackiness,fixation with nails, screws, bolts or the like becomes unnecessary forthe fixation of wall material 1 with fire-resistant sheet-like moldedarticle 2 but temporary fixation becomes possible, improving theworkability.

A composite wall material for use as a partition wall which comprises afoamed material 3 provided on both sides thereof with the fire-resistantsheet-like molded article 2, with an incombustible material 4 beingfurther provided on each external side, is schematically shown in FIG.2. In the foamed material 3, there is secured a margin for expansion ofthe fire-resistants sheet-like molded article 2. The incombustiblematerial 4 is provided for the purpose of avoiding direct exposure toflames.

A structural steel covering material comprising an I-shaped structuralsteel 6 mounted on a ceiling 5 and provided on the surface thereof withthe fire-resistant sheet-like molded article 2 of the present invention,which is covered on the external side thereof with a frame member 7 forfixation, is schematically shown in FIG. 3. Between the fire-resistantsheet-like molded article 2 and the frame member 7 for fixation asmounted externally to said article, there is ensured a margin forexpansion.

A structural steel covering material comprising an I-shaped structuralsteel 6 mounted on a ceiling 5 and provided on the external surfacethereof with the fire-resistant sheet-like molded article 2 of thepresent invention, which is covered on the external side thereof with aframe member 7 for fixation, is schematically shown in FIG. 4. Betweenthe structural steel 6 and the fire-resistant sheet-like molded article2, there is secured a margin for expansion.

EXAMPLES

The following examples illustrate the present invention in furtherdetail. The present invention, however, is never limited to theseexamples.

Examples 1 to 10 and Comparative Examples 1 to 4

According to the respective formulations shown in Table 1, therespective components were subjected to melting and kneading using aroll mill or laboratory plastomill to give resin compositions. The resincompositions obtained were subjected to press molding to givefire-resistant sheet-like molded articles. The thus-obtainedfire-resistant sheet-like molded articles were measured for specificvalues, namely A ΔT (t), load at breaking point, expansion ratio, bulkdensity, heat conductivity and total endothermic value, by the methodsmentioned below. The results obtained are shown in Table 1. In thetable, “−” means that no specific value measurement or evaluation testwas carried out.

In Table 1, “butyl rubber” refers to isobutylene-isoprene rubber with aMooney viscosity (100° C.) of 47 and a degree of unsaturation of 2.0;“chloroprene” to Skyprene B-11 (product of Tosoh Corp.); “chlorinatedbutyl” to chlorinated butyl rubber (product of Exxon Chemical) with aMooney viscosity (125° C.) of 38 and a degree of chlorination of 1.2%;“metallocene polyethylene” to EG8200 (product of Dow); “polybutene” topolybutene 100R (product of Idemitsu Petrochemical); “liquidchloroprene” to HO50 (product of Denki Kagaku Kogyo); “hydrogenatedpetroleum resin” to Escorez #5320 (product of Exxon); “ammoniumpolyphosphate” to AP-422 (product of Hoechst); “red phosphorus” to aproduct of Hoechst; “neutralized, thermally expandable graphite” toGREP-EG (product of Tosoh); “aluminum hydroxide” to H-42M (product ofShowa Denko); “magnesium hydroxide” to Kisuma 5B (product of KyowaChemical); “calcium carbonate” to Whiton 5B (product of ShiraishiCalcium); “strontium carbonate” to a product of Sakai Chemical Industry;“pentaerythritol” to a product of Mitsui Toatsu Chemical; “polyvinylalcohol (PVA)” to Poval PVA-117S (product of Kuraray); and “glass fiber”to glass fiber with a fiber diameter of 13 μm and a fiber length of 6mm.

Methods of Measuring Specific Values

(1) ΔT (t)

After measurement of the initial thickness t (mm) with a test specimenhaving a length of 50 mm and a width of 50 mm, this test specimen wasplaced on a hot plate heated to 500° C. and heated for 60 minutes, andthe temperature of the reverse side of the test specimen was measured.The difference ΔT (° C.) between the heated surface temperature and thereverse side temperature was calculated as follows:

ΔT=500−(reverse side temperature).

When the results obtained were represented graphically, with thetemperature difference ΔT (° C.) between the heated surface temperatureand the reverse side temperature on the ordinate and the initialthickness t (mm) on the abscissa and the relation

ΔT≧0.015t⁴−0.298t³+1.566t²+30.151t,

as indicated by an oblique line in FIG. 5 and said relation wassatisfied, the evaluation result was shown as ∘ and when said relationwas not satisfied, as X, under the specific value heading ΔT (t) inTable 1.

(2) Load at Breaking Point

A specimen, 10 cm in length, 10 cm in width and 0.3 cm in initialthickness, was burned in a horizontally orientation for 30 minutes bysupplying radiant heat flux of 50 kW/cm² using a cone calorimeter (CONE2A, product of Atlas). The load at breaking point of the residue uponheating was measured by compressing the residue on heating at a rate of0.1 cm/s using a microcompression tester (product of Kato Tech). When nobreaking point was found, the test result was indicates as X.

(3) Expansion Ratio

A specimen, 10 cm in length, 10 cm in width and 0.3 cm in initialthickness, was burned in a horizontally orientation for 30 minutes byradiating heat flux of 50 kW/cm² using a cone calorimeter (CONE2A,product of Atlas). The thickness t′ after heating was measured and t′/twas calculated.

(4) Bulk Density

A specimen, 10 cm in length, 10 cm in width and 0.3 cm in initialthickness, was burned in a horizontally orientation for 30 minutes byradiating heat flux of 50 kW/cm² using a cone calorimeter (CONE 2A,product of Atlas) and then the test specimen residue was measured forchange in thickness and for change in weight. The bulk density beforeheating and that after heating were calculated as follows:

Bulk density before heating (g/cm³)=weight before heating/(10×10×initialthickness (cm))

Bulk density after heating (g/cm³)=weight after heating/(10×10×thicknessafter heating (cm))

(5) Heat Conductivity

A specimen, 10 cm in length, 10 cm in width and 0.30 cm in thickness,was burned in a horizontally orientation for 30 minutes by radiatingheat flux of 50 kW/cm² using a cone calorimeter (CONE 2A, product ofAtlas) and then the heat conductivity of the test specimen residue wasmeasured by the flat sheet heat flow meter method according to JIS A1412.

(6) Total Endothermic Value

Using a differential scanning calorimeter (DSC 220, product of SeikoElectronic Industry), the total endothermic value was measured with atest specimen weighing 10 mg by raising the temperature from ordinarytemperature to 600° C. at a rate of 10° C./min.

The fire-resistant sheet-like molded articles obtained were evaluatedfor certain performance characteristics, namely flame retardancy, shaperetention, tackiness, workability and moldability, in the followingmanner. The results are shown in Table 1.

Performance Characteristics Evaluation

(1) Flame Retardancy

Evaluation 1A

A 25-mm-thick ALC board for use as an external wall, and a wall materialcomprising a laminate composed of a 20-mm-thick ALC board for use as anexternal wall and a initially 5-mm-thick fire-resistant sheet-likemolded article, covered with a wire net having a wire diameter of 0.5 mmwere subjected to flame retardancy testing.

For flame retardancy evaluation, a fire-resistant furnace was used, andthe furnace temperature was raised to 925° C. over 1 hour according toJIS A 1304 and then the reverse side temperature of the external wallALC board was measured. When the reverse side temperature was not higherthan 260° C., the result was indicated by ∘ and when it was above 260°C., by X.

As a result, in spite of the equal total thickness of 25 mm, the reverseside temperature of the external wall ALC board alone exceeded 260° C.,which is the standard for external wall materials whereas, in the caseof the external wall material having the fire-resistant sheet-likemolded article attached in the manner of lamination, said temperaturewas 250° C.

Evaluation 1B

A sample prepared by covering an H-shaped heavy weight structural steel,200×400×5,400 mm in size, with a 12-mm-thick ceramic blanket followed bywelding fixation using duct pins, and a sample prepared by laminatingthe same steal material and a fire-resistant sheet-like molded articlehaving an initial thickness of 6 mm, followed by further covering with a6-mm-thick ceramic blanket, followed by welding fixation using duct pinswere measured for the structural steel temperature of said heavy weightstructural steel in a fire-resistant furnace according to JIS A 1304 assame as Evaluation 1A. When the reverse side temperature was not higherthan 260° C., the result was indicated by ∘ and, when it was higher than260° C., the result was indicated by X.

As a result, in spite of the equal total covering thickness of 12 mm,the temperature of the structural steel covered with the ceramic blanketalone was 600° C. on average, namely greatly higher than the standardvalue of 350° C. whereas, with the heavy weight structural steel coveredwith the fire-resistant sheet-like molded article, the temperature was340° C. on average.

The same H-shaped heavy weight structural steel was spray-coated to havethickness of 12 mm with a spray coating composition composed of 35% byweight of aluminum hydroxide, 25% by weight of Portland cement, 20% byweight of calcium carbonate, 7% by weight of vermiculite, 8% by weightof pearlite, 3% by weight of a silicate salt powder and 1% by weight ofglass fiber. Although the resulting coating satisfied the fire-resistantperformance requirement, an hour was required until completion of thespray coating operation and a mask was necessary to wear during theprocedure, hence the workability was very poor.

It was found that those satisfying the relation

ΔT≧0.015t⁴−0.298t³+1.566t²+30.151t,

among the above-mentioned specific values, were those with whichsatisfactory results were obtained in both the heat resistanceevaluation tests 1A and 1B. The cases in which the above relation wasnot satisfied were those in which unsatisfactory results were obtainedin either of the above flame retardancy evaluation tests 1A and 1B.

(2) Shape Retention

The residue on heating as obtained in the above load at breaking pointmeasurement was evaluated as ⊚ when the shape was maintained, as ∘ whenthe shape was slightly maintained, and as X when no shape wasmaintained. As a result, those showing a load at breaking point of notless than 0.05 kg/cm² were good in shape retention. In particular, thoseshowing a showing load at breaking point of not less than 3.0 kg/cm²were excellent in shape retention.

The fire-resistant sheet-like molded article of Example 1, which showeda load at breaking point of 3.2 kg/cm², gave, after heating and burning,a test residue high in shape retention; even when the sheet was stoodvertically, the test residue after heating and burning did notdisintegrate but the fire-resisting and heat-insulating layer wasretained.

(3) Tackiness

A steel ball having a diameter of {fraction (5/32)} inch was allowed tofall in an atmosphere maintained at 23° C. by the Dow ball method. Whenthe ball stopped on the fire-resistant sheet-like molded article, thetackiness was indicated by ∘ and, when the ball rolled down from themolded article, by X.

Those fire-resistant sheet-like molded articles which were given ∘ inthis evaluation could be temporality fixed on substrates to be covered,such as a structural steel, wall material and column, through their owntackiness, without falling owing to their own weight.

(4) Workability

Those with which the solvent scattered or a dust was generated and thoserequiring a time for drying after application or mounting were given theevaluation X.

(5) Moldability

The resin composition obtained was subjected to sheet-like moldedarticle by extrusion. When the extrudate maintained the form of a sheet,the composition was given ∘ and, when the sheet-like molded articlecould not be maintained, the composition was given X.

Comparative Examples 5 and 6

According to the respective formulations shown in Table 1, therespective components were subjected to melting and kneading using aroll mill or laboratory plastomill to give resin compositions. The resincompositions obtained were subjected to specific values measurement andperformance evaluation in the same manner as in Examples 1 to 10 exceptthat putties were prepared from the resin compositions obtained. Theresults are shown in Table 1.

The resin compositions of Comparative Examples 5 and 6, upon heating,took the form of a very fragile powder. The bulk densities after heatingwere calculated by collecting the powder and measuring the volume usinga cylinder.

Comparative Example 7

A fire-resisting coating composition called “Unitherm” (product ofFurukawa Technomaterial) composed of a peptide bond-containing organicsubstance, a silicate salt and a hydrocarbon compound was subjected tospecific values measurement and performance evaluation in the samemanner as in Examples 1 to 10. The results are shown in Table 1.

Comparative Example 8

A fire-resisting coating composition called “Taikarit” (product ofNippon Paint) composed of an acrylate ester-styrene polymer, ammoniumphosphate, titanium oxide and anhydrous silicic acid was subjected tospecific values measurement and performance evaluation in the samemanner as in Examples 1 to 10. The results are shown in Table 1.

Comparative Example 9

A calcium silicate board (product of Nichiasu) was subjected to specificvalues measurement and performance evaluation in the same manner as inExamples 1 to 10. The results are shown in Table 1.

TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 Formulation/Weight parts Butylrubber 42 42 42 42 42 42 — — — 42 Chloroprene — — — — — — — 60 — —Chlorinated butyl — — — — — — — — 100 — Metallocene polyethylene — — — —— — 100 — — — Polybutene 50 50 50 50 50 50 — — — 50 Liquid chloroprene —— — — — — — 35 — — Hydrogenated petroleum resin 8 8 8 8 8 8 — 5 — 8Ammonium polyphosphate 100 100 100 100 100 100 100 — 100 100 Redphosphorus — — — — — — — 100 — — Neutralized, thermally expandable — 5 55 8 8 — — 8 — graphite Aluminum hydroxide — — 50 100 100 200 — 50 — —Magnesium hydroxide — — — — — — — — 50 — Calcium carbonate 100 100 50 —— — 100 50 — 100 Strontium carbonate — — — — — — — — — — Pentaerythritol50 50 50 50 — — 50 — — — PVA — — — — — — — 100 — — Glass fiber — — — — —— — — — — Specific value Initial thickness (mm) 3 3 3 4 2 3 3 3 5 3 Δ T(t) ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Load at breaking point (kg/cm²) 3.2 4.4 4.5 30.9 ≧5 3.5 ≧5 1 4 Expansion ratio 4.2 4.3 4.1 2.5 4.6 2.9 4 3.9 4.4 3.9Bulk density before heating 1.34 1.33 1.4 1.4 1.4 1.56 1.33 1.45 1.41.37 (g/cm²) Bulk density after heating 0.14 0.13 0.15 0.15 0.16 0.210.14 0.2 0.16 — (g/cm²) Heat conductivity before heating 0.43 0.42 0.380.37 0.38 0.37 0.4 0.45 0.37 0.43 (kcal/mh ° C.) Heat conductivity afterheating 0.05 0.05 0.09 0.1 0.1 0.09 0.1 0.1 0.1 0.06 (kcal/mh ° C.)Total endtherm (J/mg) — — 150 300 340 510 — 130 170 — Evaluation Fireresistance evaluation 1A ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ — Fire resistance evaluation1B ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ — Shape retention ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚ ⊚ ◯ ⊚ Tackiness ◯ ◯◯ ◯ ◯ ◯ — — ◯ ◯ Workability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Moldability ◯ ◯ ◯ ◯ ◯ ◯◯ ◯ ◯ ◯ Comparative Example 1 2 3 4 5 6 7 8 9 Formulation/Weight partsButyl rubber 42 — — 42 — — Refractory Refractory Calusium coatingcoating silicateboard Chloroprene — — 42 — — — Chlorinated butyl — — — —— — Metallocene polyethylene — 100 — — — — Polybutene 50 — — 50 100 100Liquid chloroprene — — 50 — — — Hydrogenated petroleum resin 8 — 8 8 — —Ammonium polyphosphate 50 10 10 100 200 300 Red phosphorus — — — — — —Neutralized, thermally expandable 150 5 5 — 200 150 graphite Aluminumhydroxide — — — — — — Magnesium hydroxide — — 10 — — — Calcium carbonate— — — 800 — — Strontium carbonate — — — — — — Pentaerythritol — — — 50 —— PVA — — — — — — Glass fiber — — — — — — Specific value Initialthickness (mm) 5 5 5 — 1 3 1 2 25 Δ T (t) — — — — × × ◯ ◯ × Load atbreaking point (kg/cm²) × × × — × × × × ≧5 Expansion ratio 10 1.2 1.3 —≧30 ≧30 10 30 1 Bulk density before heating — — — — 1.5 1.55 — — 0.04(g/cm²) Bulk density after heating — — — — 0.03 0.04 — — 0.04 (g/cm²)Heat conductivity before heating — — — — — — — — 0.05 (kcal/mh ° C.)Heat conductivity after heating — — — — — — — — 0.05 (kcal/mh ° C.)Total endtherm (J/mg) — — — — — — — — 0.05 Evaluation Fire resistanceevaluation 1A × × × — × × ◯ ◯ ◯ Fire resistance evaluation 1B × × × — ×× ◯ ◯ ◯ Shape retention × × × — × × × × ⊚ Tackiness — — — — — — — — ×Workability ◯ ◯ ◯ ◯ ◯ ◯ × × ◯ Moldability ◯ × × × × × — — —

Examples 11 to 22 and Comparative Examples 10 to 12

According to the respective formulations shown in Table 2, therespective components were subjected to melting and kneading using aroll mill or laboratory plastomill to give resin compositions. The resincompositions obtained were subjected to press molding to givefire-resistant sheet-like molded articles. The thus-obtainedfire-resistant sheet-like molded articles were subjected to specificvalues measurement and performance evaluation in the same manner as inExamples 1 to 10. The results are shown in Table 2. In Examples 11 to 18and Comparative Examples 10 and 12, the expansion ratio was evaluatedaccording to the criteria: ∘ when it was within the range of 1.1 to 20.

In Table 2, the gypsum used was grade B gypsum produced by San-esuGypsum, the calcium carbonate used in Examples 14, 15 and 18 andComparative Example 10 and 12 was Whiton SB red (1.8 μm, product ofShiraishi Calcium), and in Examples 12, 13 and 17 and ComparativeExamples 11, it was Whiton BF200 (8 μm, product of Shiraishi Calcium).In Examples 19 to 22, the aluminum hydroxide used was H-31 (product ofShowa Denko), and the calcium carbonate used was Whiton BF300 (productof Shiraishi Calcium). In Example 20, polybutene #300R (product ofIdemitsu Petrochemical) was used as the polybutene. In Example 20, thebutyl rubber used was composed of 20 parts by weight #065 and 22 partsby weight of #268, in Example 21, 42 parts by weight of #268 as thebutyl rubber and, in Example 22, the butyl rubber used was composed of30 parts by weight of #065 and 12 parts by weight of Escolant 10. Theother components were the same as those used in Examples 1 to 10.

As a result, the fire-resistant sheet-like molded articles ofComparative Examples 10 and 12 showed sagging upon burning, wherebytheir thicknesses were reduced. The fire-resistant sheet-like moldedarticle of Comparative Example 11 became a powder-like residue and nobreaking point was observed.

TABLE 2 Example Comp. Ex. 11 12 13 14 15 16 17 18 19 20 21 22 10 11 12Formulation/Weight parts Butyl rubber 42 — 42 — 42 42 — 42 42 42 42 4242 42 42 Chloroprene — — — — — — — — — — — — — — — Chlorinated butyl — —— 50 — — — — — — — — — — — Metallocene polyethylene — 100 — — — — 100 —— — — — — — — Polybutene 50 — 50 45 50 50 — 50 50 50 50 50 50 50 50Liquid chloroprene — — — — — — — — — — — — — — — Hydrogenated petroleumresin 8 — 8 5 8 8 — 8 8 8 8 8 8 8 8 Ammonium polyphosphate 90 120 100100 100 90 120 100 100 100 100 100 150 10 100 Neutralized, thermallyexpandable graphite — — — — — — — — 20 20 20 20 — — — Aluminum hydroxide— — — 20 — 50 40 25 100 100 100 100 — — — Calcium carbonate — 120 100 8050 — 60 60 100 100 100 100 50 90 20 Strontium carbonate 110 — — — — 50 —— — — — — — — — Gypsum — — 10 — 50 — — 25 — — — — — — 80 Specific valueInitial thickness (mm) 3 2 2 4 3 3 4 3 2 3 3 3 5 2 3 Δ T (t) ◯ ◯ ◯ ◯ ◯ ◯◯ ◯ ◯ ◯ ◯ ◯ × × × Load at breaking point (kg/cm²) 2.7 4.5 4.2 3.2 2.012.5 4.01 2.8 1.6 3.4 4.5 4.7 × × × Expansion ratio ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ 8.84.1 4.2 4.1 × × × Bulk density before heating (g/cm²) 1.38 1.5 1.4 1.11.38 1.38 1.4 1.4 1.601 1.601 1.601 1.601 — — — Bulk density afterheating (g/cm²) — — — — — — — — 0.13 0.13 0.13 0.13 — — — Heatconductivity before heating 0.44 0.46 0.44 0.45 0.43 0.44 0.46 0.440.501 0.501 0.501 0.501 — — — (kcal/mh ° C.) Heat conductivity afterheating 0.07 0.08 0.07 0.08 0.08 0.07 0.08 0.07 0.09 0.09 0.09 0.09 — —— (kcal/mh ° C.) Total endtherm (J/mg) — — — — — — — — 300 300 300 300 —— — Evaluation Fire resistance evaluation 1A ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ — —— Fire resistance evaluation 1B ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ — — — Shaperetention ◯ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ◯ ◯ ⊚ ⊚ ⊚ × × × Tackiness ⊚ — ⊚ ⊚ ⊚ ⊚ — ⊚ ⊚ ⊚ ⊚⊚ — — — Moldabilty ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ — — —

Examples 23 to 28 and Comparative Examples 13 to 16

According to the respective formulations shown in Table 3, therespective components were subjected to melting and kneading using aroll mill to give resin compositions. The resin compositions obtainedwere subjected to press molding at 140° C. to give fire-resistantsheet-like molded articles. The thus-obtained fire-resistant sheet-likemolded articles were measured for tackiness, reverse side temperature,holding power and flame retardancy by the methods mentioned below. Theresults obtained are shown in Table 3.

In Table 3, Exxon Butyl #065 (product of Exxon Chemical) was used as“butyl rubber 1”; Escolant #10 (product of Exxon Chemical) was used as“butyl rubber 2”; Exxon Butyl #268 (product of Exxon Chemical) was usedas “butyl rubber 3”; a product of Japan Synthetic Rubber was used as“styrene-butadiene rubber”; Escorez #5320 (product of Exxon Chemical)was used as “tackifier resin”; Polybutene 100R (product of IdemitsuPetrochemical) was used as “polybutene”; GREP-EG (product of Tosoh) wasused as “neutralized, thermally expandable graphite”; AP-422 (product ofHoechst) was used as “ammonium polyphosphate”; a product of Wako PureChemical was used as “t-butylphosphonic acid”; Hygillite H-42M (productof Showa Denko) was used as “aluminum hydroxide”; and Kisuma 5B (productof Kyowa Chemical) was used as “magnesium hydroxide”. In Table 3,“TeEDC” stands for tellurium diethyldithiocarbamate, and “MBTS” fordibenzothiazyl sulfide.

Performance Evaluation

(1) Tackiness

Fire-resistant sheet-like molded articles having an initial thickness of4 mm were prepared and evaluated by the ball tack method according toJIS Z 0237.

(2) Reverse Side Temperature

One side of each test specimen (100 mm in length, 100 mm in width, 4 mmin initial thickness) placed on a stainless steel plate (100 mm inlength, 100 mm in width) was heated to 500° C. on a hot plate and, thereverse side temperature was measured. As a result, those which showed atemperature below 260° C. were given ∘, and those which showed atemperature not lower than 260° C. were given X.

(3) Holding Power

The fire-resistant sheet-like molded article having an initial thicknessof 4 mm was cut to 25-mm-wide strips. The back side of each strip wasprovided by lamination with a 38-μm-thick polyester film and theresulting strip was sticked on a polished stainless steel plateaccording to JIS Z 0237. After 20 minutes of standing, the whole wasallowed to stand in a constant temperature oven maintained at 180° C.for 20 minutes, a 100-g weight was suspended therefrom and the timerequired for the weight to drop was measured.

(4) Flame Retardancy

A test specimen of the fire-resistant sheet-like molded article havingan initial thickness of 4 mm was sticked to a 0.5-mm-thick stainlesssteel sheet, and the other side of the test specimen was provided with alath so that a distance of mm was maintained between the lath and a SUSsheet, and the test specimen was radiated with radiant heat flux of 50kW/cm² from the SUS sheet side for 30 minutes using a cone calorimeter(CONE 2A, product of Atlas) (in the horizontal direction). When the backside temperature after 30 minutes was lower than 260° C. and noabnormality was observed in appearance, the test specimen was given ∘and, when the back side temperature was not lower than 260° C. or anabnormality in appearance, for example formation of through holes as aresult of sagging, was observed, it was given X.

TABLE 3 Example Comp. Ex. 23 24 25 26 27 28 13 14 15 16Formulation/Weight parts Butyl rubber 1 42 40 — — — — 42 — — 30 Butylrubber 2 — — 35 35 — — — — — — Butyl rubber 3 — — — — 45 — — — — —Styrene-butadiene rubber — — — — — 50 — 45 100 — Tackifier resin 8 10 1015 10 15 8 10 — 10 Polybutene 50 50 55 50 45 35 50 45 — 60 Neutralized,thermally 30 100 10 30 5 8 20 20 100 100 expandable graphite Ammoniumpolyphosphate 20 50 10 — 150 100 — 15 50 50 t-Butylphosphoric acid — — —50 — — — — — — Aluminum hydroxide 150 — 100 — — — 100 — 600 — Magnesiumhydroxide — 50 — 70 45 100 — — — 100 Sulfur — — — — 0.4 0.8 — 0.4 — —TeEDC — — — — 0.4 0.4 — 0.4 — — MBTS — — — — 0.4 0.8 — 0.4 — —Evaluation Tackiness 32 32 32 32 28 28 32 32 <23 32 Reverse side temp. ◯◯ ◯ ◯ ◯ ◯ × × ◯ ◯ Holding power >30 >30 >30 >30 >30 >30 >30 >30 <1 7Fire resistance evaluation ⊚ ⊚ ⊚ ⊚ ◯ ◯ × × × ×

Comparative Example 17

A fire-resistant sheet-like molded article was produced and evaluated inthe same manner as in Example 23 except that, in the composition ofExample 23, Polybutene OH (product of Idemitsu Petrochemical) with anaverage molecular weight of 3.50 was used in lieu of Polybutene 100R.

As a result, the tackiness was 32 and the reverse side temperature inthe horizontal orientation was lower than 260° C., thus the results weregood in these respects, but the test specimen fell after 5 minutes inthe holding power test. In the flame retardancy test, the fire-resistantsheet-like molded article broke and fell down after 10 minutes and thereverse side temperature exceeded 260° C.

Examples 29 and 30

Following the formulation of Example 28, 4-mm-thick sheets were moldedon a press at 90° C. Two of these sheets were piled up and pressed on apress at 140° C. to give a 7-mm-thick fire-resistant sheet-like moldedarticle (Example 29). Further, three of said sheets were piled up andmoled into a 11-mm-thick fire-resistant sheet-like molded article in thesame manner (Example 30).

As a result, both held for at least 1 hour in the holding power test andgave good results in the tackiness, reverse side temperature and flameretardancy tests as well.

Example 31

Sheets having a thickness of 2 mm were molded by compounding accordingto the formulation of Example 28 except that the addition of sulfur,TeEDC and MBTS was omitted, and press-molding on a press at 90° C. Awoven glass fiber fabric (Asahi Fiber Glass' HS180) was sandwichedbetween two of said sheets in the form of a three-layer laminate,followed by pressing on a press at 140° C. to give a 4-mm-thickfire-resistant sheet-like molded article.

As a result, it gave good results in the holding power, tackiness,reverse side temperature and flame retardancy tests.

Examples 32 to 37 and Comparative Examples 18 to 21

According to the respective formulations shown in Table 4,fire-resistant sheet-like molded articles were produced in the samemanner as in Examples 23 to 28 and evaluated for tackiness, reverse sidetemperature, holding power and flame retardancy. The results are shownin Table 4.

TABLE 4 Example Compar. Ex. 32 33 34 35 36 37 18 19 20 21Formulation/Weight parts Butyl rubber 1 42 40 — — — — 42 — 42 — Butylrubber 2 — — 35 35 — — — — — — Butyl rubber 3 — — — — 45 — — — — 45Styrene-butadiene rubber — — — — — 50 — 45 — — Tackifier resin 8 10 1015 10 15 8 10 8 10 Polybutene 50 50 55 50 45 35 50 45 50 45Dipentaerythritol 50 — — 60 50 50 10 50 200 10 D-Sorbitol — 50 — — — — —— — — Corn starch — — 50 — — — — — — — Ammonium polyphosphate 100 100 75— 30 100 20 100 200 20 t-Butylphosphonic acid — — — 60 — — — — — —Aluminum hydroxide — — 100 — 150 — 50 — 600 50 Magnesium hydroxide — 100— 100 — 100 — — — — Sulfur — — — — 0.4 0.8 — — — 0.4 TeEDC — — — — 0.40.4 — — — 0.4 MBTS — — — — 0.4 0.8 — — — 0.4 Evaluation Tackiness 30 3032 32 28 27 30 32 <2 30 Reverse side temp. ◯ ◯ ◯ ◯ ◯ ◯ × ◯ ◯ × Holdingpower >30 >30 >30 >30 >30 >30 >30 <1 <1 >30 Fire resistance evaluation ⊚⊚ ⊚ ⊚ ◯ ◯ × × × ×

Comparative Example 22

A fire-resistant sheet-like molded article was produced and evaluated inthe same manner as in Example 32 except that, in the composition ofExample 32, Polybutene OH (product of Idemitsu Petrochemical) with anaverage molecular weight of 350 was used in lieu of Polybutene 100R.

As a result, the tackiness was 32 and the reverse side temperature inthe horizontal orientation was lower than 260° C., thus the results weregood in these respects, but the test specimen fell after 5 minutes inthe holding power test. In the flame retardancy test, the fire-resistantsheet-like molded article broke and fell down after 10 minutes and thereverse side temperature exceeded 260° C.

Examples 38 and 39

Following the formulation of Example 37, 4-mm-thick sheets were moldedon a press at 90° C. Two of these sheets were piled up and pressed on apress at 140° C. to give a 7-mm-thick fire-resistant sheet-like moldedarticle (Example 38). Further, three of said sheets were piled up andmolded into a 11-mm-thick fire-resistant sheet-like molded article inthe manner as same as Example 39.

As a result, both held for at least 1 hour in the holding power test andgave good results in the tackiness, reverse side temperature and flameretardancy tests as well.

Example 40

Sheets having a thickness of 2 mm were molded by compounding accordingto the formulation of Example 37 except that the addition of sulfur,TeEDC and MBTS was omitted, and press-molding on a press at 90° C. Awoven glass fiber fabric (Asai Fiber Glass' HS180) was sandwichedbetween two of said sheets in the form of a three-layer laminate,followed by pressing on a press at 140° C. to give a 4-mm-thickfire-resistant sheet-like molded article.

As a result, it gave good results in the holding power, tackiness,reverse side temperature and flame retardancy tests.

INDUSTRIAL APPLICABILITY

The fire-resistant sheet-like molded article of the present invention,which has the constitution mentioned hereinabove, can take advantage ofthe characteristics resulting from the adhesiveness possessed by thefire-resistant sheet-like molded article at ordinary temperature andtherefore excellent in workability and, when heated, can expand andthereby produce thermal insulating effects and, in addition, can produceexcellent fire-resisting effects since the residue after combustion hassufficient shape-retaining properties.

What is claimed is:
 1. A fire-resistant sheet molded article comprisinga resin composition and having the relationship between the initialthickness t (mm) and the temperature difference Δ_(T) (° C.) between oneside and the reverse side after heating of said one side at 500° C. for1 hour as represented by: Δ_(T)≧0.015t⁴−0.298t³+1.566t²+30.151t, andhaving the initial bulk density at 25° C. of 0.8 to 2.0 g/cm³ and thebulk density after 1 hour of heating at 500° C. of 0.05 to 0.5 g/cm³. 2.The fire-resistant sheet molded article according to claim 1, whereinthe initial thickness is 0.5 to 20 mm.
 3. The fire-resistant sheetmolded article according to claim 1, wherein the initial thickness t(mm) and the thickness t′ (mm) after 30 minutes of heating under radiantheat flux of 50 kW/cm² are in the relation of t′/t=1.1 to
 20. 4. Thefire-resistant sheet molded article according to claim 1, wherein theresin composition comprises a thermoplastic resin, a phosphoruscompound, neutralized, thermally expandable graphite and an inorganicfiller, the total content of said phosphorus compound and neutralized,thermally expandable graphite being 20 to 300 parts by weight and thecontent of said inorganic filler being 50 to 500 parts by weight, per100 parts by weight of said thermoplastic resin, the weight ratio ofsaid neutralized, thermally expandable graphite to said phosphoruscompound (neutralized, thermally expandable graphite/phosphoruscompound) being 0.01 to
 9. 5. The fire-resistant sheet molded articleaccording to claim 1, wherein the resin composition comprises athermoplastic resin, a phosphorus compound, a hydroxyl-containinghydrocarbon compound and inorganic filler, the total content of saidphosphorus compound, hydroxyl containing hydrocarbon compound andinorganic filler being 50 to 900 parts by weight per 100 parts by weightof said thermoplastic resin, the weight ratio of saidhydroxyl-containing hydrocarbon compound to said phosphorus compound(hydroxyl-containing hydrocarbon compound/phosphorus compound) being0.05 to
 20. 6. The fire-resistant sheet molded article according toclaim 1, wherein the resin composition comprises a thermoplastic resin,phosphorus compound, neutralized, thermally expandable graphite, ahydroxyl-containing hydrocarbon compound and an inorganic filler, thetotal content of said phosphorus compound, neutralized, thermallyexpandable graphite, hydroxyl-containing hydrocarbon compound andinorganic filler being 50 to 900 parts by weight per 100 parts of weightof said thermoplastic resin, the weight ratio of said neutralized,thermally expandable graphite to said phosphorus compound (neutralized,thermally expandable graphite/phosphorus compound) being 0.01 to 9 andthe weight ratio of said hydroxyl-containing hydrocarbon compound tosaid phosphorus compound (hydroxyl-containing hydrocarboncompound/phosphorus compound) being 0.05 to
 20. 7. The fire-resistantsheet molded article according to claim 1, wherein the resin compositioncomprises a thermoplastic resin, a phosphorus compound and a metalcarbonate, the total content of said phosphorus compound and metalcarbonate being 50 to 900 parts by weight per 100 parts by weight ofsaid thermoplastic resin, the weight ratio between said metal carbonateand phosphorus compound (metal carbonate: phosphorus compound) being 6:4to 4:6.
 8. The fire-resistant sheet molded article according to claim 1,wherein the resin composition comprises a thermoplastic resin, aphosphorus compound and a metal carbonate and, further comprises ahydrated inorganic compound and/or a calcium salt, the total content ofsaid phosphorus compound, metal carbonate and hydrated inorganiccompound and/or calcium salt being 50 to 900 parts by weight per 100parts by weight of said thermoplastic resin, the total content of saidhydrated inorganic compound and/or calcium salt being 1 to 70 parts per100 parts by weight of said metal carbonate, the weight ratio of the sumof said metal carbonate and hydrated inorganic compound and/or calciumsalt to said phosphorus compound (the sum of metal carbonate andhydrated inorganic compound and/or calcium salt:phosphorus compound)being 6:4 to 4:6.
 9. The fire-resistant sheet molded article accordingto claim 1, wherein the resin composition comprises a thermoplasticresin, a phosphorus compound, neutralized, thermally expandablegraphite, hydrated inorganic compound and a metal carbonate, the totalcontent of said phosphorus compound and neutralized, thermallyexpandable graphite being 20 to 300 parts by weight, the content of saidmetal carbonate being 10 to 500 parts by weight and the content of saidhydrated inorganic compound being 10 to 500 parts by weight, per 100parts by weight of said thermoplastic resin, the weight ratio of saidneutralized, thermally expandable graphite to said phosphorus compound(neutralized, thermally expandable graphite/phosphorus compound) being0.01 to
 9. 10. The fire resistant sheet molded article according toclaim 1, wherein the resin composition comprises a rubber composition.11. The fire-resistant sheet molded article according to claim 10,wherein the rubber composition comprises 30 to 70 parts by weight of arubber having a Mooney viscosity at 100° C. of not less than 40 and 70to 30 parts by weight of a liquid resin having an average molecularweight of 500 to 10,000.
 12. The fire-resistant sheet molded articleaccording to claim 1, wherein the resin composition has tackiness. 13.The fire-resistant sheet molded article according to claim 1, whereinthe resin composition is crosslinked.
 14. A fire-resistant sheet moldedarticle which comprises a laminate comprising the fire-resistantsheet-like molded article according to claim 10, and a reinforcingsubstrate further mounted thereon, and which has tackiness on one orboth sides.
 15. A fire-resistant laminate for covering structural steelwhich comprises a laminate comprising the fire-resistant sheet moldedarticle according to claim 1 and a sheet (a) capable of retaining theshape of said fire-resistant sheet molded article without preventingsaid fire-resistant sheet-like molded article from expanding and capableof shielding said molded article from flames.
 16. A fire-resistantstructural material for wall which comprises the fire-resistant sheetmolded article according to claim 1, mounted on at least one side of aboard having a thickness of 0.5 to 100 mm.
 17. A fire-resistantstructural material for wall which comprises the fire-resistant sheetmolded article according to claim 1, mounted on at least one side of aboard having a thickness of 0.5 to 100 mm, and a material (b), furthermounting thereon, capable of retaining the shape of said fire-resistantsheet-like molded article without preventing said fire-resistant sheetmolded article from expanding.
 18. A method of fabricating afire-resistant structural steel which comprises covering the surface ofa structural steel which comprises covering the surface of a structuralsteel with the fire-resistant sheet molded article according to claim 1,and further covering thereon with a sheet (a) capable of retaining theshape of said fire-resistant sheet molded article without preventingsaid fire-resistant sheet molded article from expanding and capable ofshielding said molded article from flames by using tackiness of saidfire-resistant sheet-line molded article.
 19. A method of fabricating afire-resisting wall which comprises mounting the fire-resistant sheetmolded article according to claim 1, on at least one side of a wallmaterial and further mounting thereon a material (b) capable ofretaining the shape of said fire-resistant sheet molded article withoutpreventing said fire-resistant sheet molded article from expanding,wherein a unit composed of said fire-resistant sheet molded article andsaid material (b) in advance is used.
 20. A fire-resistant sheet moldedarticle which comprises a laminate comprising the fire-resistant sheetmolded article of claim 10, and reinforcing substrate further mounted onboth sides thereof to form a double tacky sheet.
 21. A fire-resistantsheet molded article which comprises a laminate of the fire-resistantsheet molded article according to claim 10, and reinforcing substrate,further mounted thereon, made of polypropylene, polyester, nylon orcellulose fiber or the like and which has tackiness on one or bothsides.
 22. A fire-resistant laminate for covering structural steel whichcomprises a laminate comprising the fire-resistant sheet molded articleaccording to claim 1, and a sheet (a) capable of retaining the shape ofsaid fire-resistant sheet molded article without preventing saidfire-resistant sheet molded article from expanding and capable ofshielding said molded article from flames, wherein said sheet (a) is aceramic blanket.
 23. A fire-resistant laminate for covering structuralsteel which comprises a laminate comprising the fire-resistant sheetmolded article according to claim 4, and a sheet (a) capable ofretaining the shape of said fire-resistant sheet molded article withoutpreventing said fire-resistant sheet molded article from expanding andcapable of shielding said molded article from flames.
 24. Afire-resistant structural material for wall which comprises thefire-resistant sheet molded article according to claim 4, mounted on atleast one side of a board having a thickness of 0.5 to 100 mm.
 25. Awall-forming fire-resistant structural material which comprises thefire-resistant sheet molded article according to claim 4, mounted on atleast one side of a board having a thickness of 0.5 to 100 mm, and amaterial (b), further mounted thereon, capable of retaining the shape ofsaid fire-resistant sheet-like molded article without preventing saidfire-resistant sheet-like molded article from expanding.
 26. A method offabricating a fire-resistant structural steel which comprises coveringthe surface of the structural steel with the fire-resistant sheet moldedarticle according to claim 4, and further covering thereon with a sheet(a) capable of retaining the shape of said fire-resistant sheet moldedarticle without preventing said fire-resistant sheet molded article fromexpanding and capable of shielding said molded article from flames. 27.A method of fabricating a fire-resisting wall which comprises mountingthe fire-resistant sheet molded article according to claim 4, on atleast one side of a wall material and further mounting thereon amaterial (b) capable of retaining the shape of said fire-resistant sheetmolded article without preventing said fire-resistant sheet-like moldedarticle from expanding.
 28. The fire-resistant sheet molded articleaccording to claim 1, wherein the resin component is crosslinked.
 29. Afire-resistant sheet molded article comprising a resin composition, andhaving a breaking point and the load at breaking point of not less than0.05 kg/cm² when it is subjected to volume expansion by heating underradiant heat flux of 50 kW/cm² for 30 minutes and then the combustionresidue is compressed at a rate of 0.1 cm/s.
 30. The fire-resistantsheet molded article according to claim 29, wherein the initialthickness t (mm) and the thickness t′ (mm) after 30 minutes of heatingunder radiant heat flux of 50 kW/cm² are in the relation of t′/t=1.1 to20.
 31. The fire-resistant sheet molded article according to claim 29,wherein the resin composition comprises a thermoplastic resin, aphosphorus compound, neutralized, thermally expandable graphite and aninorganic filler, the total content of said phosphorus compound andneutralized, thermally expandable graphite being 20 to 300 parts byweight and the content of said inorganic filler being 50 to 500 parts byweight, per 100 parts by weight of said thermoplastic resin, the weightration of said neutralized, thermally expandable graphite to saidphosphorus compound (neutralized, thermally expandablegraphite/phosphorus compound) being 0.01 to
 2. 32. A fire-resistantsheet molded article comprising a resin composition and showing athermal conductivity, after the volume expansion by heating underradiant heat flux of 50 kW/cm² for 30 minutes, of 0.01 to 0.3 kcal/m·h·°C.
 33. A fire-resistant sheet molded article comprising a resincomposition and showing the total endothermic value, when raising thetemperature to 600° C. at a rate of 10° C./min. by DSC, of not less than100 J/g.
 34. A fire-resistant sheet molded article comprising a resincomposition and having an initial thickness of 0.5 to 20 mm andtackiness enough to support itself under a load of 15 to 40 N/m of widthat not more than 180° C. for 30 minutes or longer.
 35. A fire-resistantsheet molded article comprising a resin composition and having therelationship between the initial thickness t (mm) and the temperaturedifference Δ_(T) (° C.) between one side and the reve rse side afterheating of said one side at 500° C. for 1 hour as represented by:Δ_(T)≧0.015t⁴−0.298t³+1.566t²+30.151t, and having the initial bulkdensity at 25° C. of 0.8 to 2.0 g/cm³ and the bulk density after 1 hourof heating at 500° C. of 0.05 to 0.5 g/cm³, wherein said resincomposition shows the total edotherm, when raising the temperature to600° C. at a rate of 10° C./min. by DSC, of not less than 100 J/g.
 36. Afire-resistant sheet molded article comprising a resin composition andhaving the relationship between the initial thickness t (mm) and thetemperature difference Δ_(T) (° C.) between one side and the reverseside after heating of said one side at 500° C. for 1 hour as representedby: Δ_(T)≧0.015t⁴−0.298t³+1.566t²+30.151t, and having said initial bulkdensity at 25° C. of 0.8 to 2.0 g/cm³ and the bulk density after 1 hourof heating at 500° C. of 0.5 to 0.5g/cm³, wherein said fire-resistantsheet-like molded article has an initial thickness of 0.5 to 20 mm andsaid resin composition has tackiness enough to support itself under aload of 15 to 40 N/m of width at more than 180° C. for 30 minutes orlonger.